Electrode binder slurry composition for lithium ion electrical storage devices

ABSTRACT

The present invention provides a slurry composition comprising a binder comprising a polymer comprising a fluoropolymer dispersed in a liquid medium; an adhesion promoter; and at least one of an electrochemically active material or an electrically conductive agent. The present invention also provides electrodes and electrical storage devices.

FIELD OF THE INVENTION

The invention relates to fluoropolymer, such as polyvinylidene fluoride(PVDF), slurry compositions for manufacturing electrodes for use inelectrical storage devices, such as batteries.

BACKGROUND OF THE INVENTION

There is a trend in the electronics industry to produce smaller devices,powered by smaller and lighter batteries. Batteries with a negativeelectrode—such as a carbonaceous material, and a positive electrode—suchas lithium metal oxides can provide relatively high power and lowweight.

Polyvinylidene fluoride, because of its excellent electrochemicalresistance, has been found to be a useful binder for forming electrodesto be used in electrical storage devices. Typically, the polyvinylidenefluoride is dissolved in an organic solvent and the electrode material,that is, the electrochemically active compound and usually anelectrically conductive material such as a carbonaceous material, iscombined with the PVDF solution to form a slurry that is applied to ametal foil or mesh to form the electrode.

The role of the organic solvent is to dissolve PVDF in order to providegood adhesion between the electrode material particles and the metalfoil or mesh upon evaporation of the organic solvent. Currently, theorganic solvent of choice is N-methyl-2-pyrrolidone (NMP). PVDF bindersdissolved in NMP provide superior adhesion and an interconnectivity ofall the active ingredients in the electrode composition. The boundingredients are able to tolerate large volume expansion and contractionduring charge and discharge cycles without losing interconnectivitywithin the electrodes. Interconnectivity of the active ingredients in anelectrode is extremely important in battery performance, especiallyduring charging and discharging cycles, as electrons must move acrossthe electrode, and lithium ion mobility requires interconnectivitywithin the electrode between particles.

Unfortunately, NMP is a toxic material and presents health andenvironmental issues. It would be desirable to replace NMP as a solventfor PVDF binders. However, NMP is somewhat unique in its ability todissolve PVDF that is not nearly as soluble in other organic solvents.

To effectively employ PVDF compositions in electrode-forming processesin organic solvent other than NMP, the PVDF must be dispersed in thesolvent. However, the dispersion must be compatible with currentmanufacturing practices and provide desired properties of theintermediate and final products. Some common criteria include: a)stability of the fluoropolymer dispersion, having sufficient shelf-life,b) stability of the slurry after admixing the electrochemically activeand/or electroconductive powders with the dispersion, c) appropriateviscosity of the slurry to facilitate good application properties, andd) sufficient interconnectivity within the electrode.

Waterborne PVDF dispersions have also been considered, but the resultingelectrode coatings often demonstrate decreased peel strength compared tosolvent-borne counterparts.

It is therefore an objective of the present invention to provide stablePVDF dispersions having good application properties for use in preparingelectrode-forming compositions, which enable production of high qualityelectrodes having interconnectivity and satisfactory peel strength forbatteries and other electrical storage devices, avoiding theafore-mentioned disadvantages associated with the use ofN-methyl-2-pyrrolidone.

SUMMARY OF THE INVENTION

The present invention provides a slurry composition comprising anelectrochemically active material; a binder comprising a polymercomprising a fluoropolymer dispersed in a liquid medium; and an adhesionpromoter.

The present invention also provides a slurry composition comprising anelectrically conductive agent; a binder comprising a polymer comprisinga fluoropolymer dispersed in a liquid medium; and an adhesion promoter.

The present invention further provides an electrode comprising anelectrical current collector; and a film formed on the electricalcurrent collector, wherein the film is deposited from a slurrycomposition comprising an electrochemically active material; anelectrically conductive agent; a binder comprising a polymer comprisinga fluoropolymer dispersed in a liquid medium; and an adhesion promoter.

The present invention also provides an electrical storage devicecomprising an electrode comprising an electrical current collector; anda film formed on the electrical current collector, wherein the film isdeposited from a slurry composition comprising an electrochemicallyactive material; an electrically conductive agent; a binder comprising apolymer comprising a fluoropolymer dispersed in a liquid medium; and anadhesion promoter; a counter electrode; and an electrolyte.

DESCRIPTION OF THE DRAWING

FIG. 1 is a graph illustrating the first derivative of Log viscosityversus temperature, wherein the peak maximum is used to determine thedissolution temperature of PVDF dispersed in 1,2,3-triacetoxypropane(triacetin) from the abscissa.

DETAILED DESCRIPTION

The present invention is directed to a slurry composition comprising anelectrochemically active material; a binder comprising a polymercomprising a fluoropolymer dispersed in a liquid medium; and an adhesionpromoter. The slurry composition may optionally further comprise adispersant and/or an electrically conductive agent.

The slurry composition comprises an electrochemically active material.The material constituting the electrochemically active materialcontained in the slurry is not particularly limited and a suitablematerial can be selected according to the type of an electrical storagedevice of interest.

The electrochemically active material may comprise a material for use asan active material for a positive electrode. The electrochemicallyactive material may comprise a material capable of incorporating lithium(including incorporation through lithium intercalation/deintercalation),a material capable of lithium conversion, or combinations thereof.Non-limiting examples of electrochemically active materials capable ofincorporating lithium include LiCoO₂, LiNiO₂, LiFePO₄, LiCoPO₄, LiMnO₂,LiMn₂O₄, Li(NiMnCo)O₂, Li(NiCoAl)O₂, carbon-coated LiFePO₄, andcombinations thereof. Non-limiting examples of materials capable oflithium conversion include sulfur, LiO₂, FeF₂ and FeF₃, Si, aluminum,tin, SnCo, Fe₃O₄, and combinations thereof.

The electrochemically active material may comprise a material for use asan active material for a negative electrode. The electrochemicallyactive material may comprise graphite, lithium titanate, siliconcompounds, tin, tin compounds, sulfur, sulfur compounds, or acombination thereof.

The electrochemically active material may be present in the slurry inamounts of 45% to 95% by weight, such as 70% to 98% by weight, based onthe total solids weight of the slurry.

According to the present invention, the binder comprises a polymercomprising a fluoropolymer dispersed in liquid medium. The fluoropolymermay serve as all or a component of the binder for the slurrycomposition.

The fluoropolymer may comprise a (co)polymer comprising the residue ofvinylidene fluoride. A non-limiting example of a (co)polymer comprisingthe residue of vinylidene fluoride is a polyvinylidene fluoride polymer(PVDF). As used herein, the “polyvinylidene fluoride polymer” includeshomopolymers, copolymers, such as binary copolymers, and terpolymers,including high molecular weight homopolymers, copolymers, andterpolymers. Such (co)polymers include those containing at least 50 molepercent, such as at least 75 mole %, and at least 80 mole %, and atleast 85 mole % of the residue of vinylidene fluoride (also known asvinylidene difluoride). The vinylidene fluoride monomer may becopolymerized with at least one comonomer selected from the groupconsisting of tetrafluoroethylene, trifluoroethylene,chlorotrifluoroethylene, hexafluoropropene, vinyl fluoride,pentafluoropropene, tetrafluoropropene, perfluoromethyl vinyl ether,perfluoropropyl vinyl ether and any other monomer that would readilycopolymerize with vinylidene fluoride in order to produce thefluoropolymer of the present invention. The fluoropolymer may alsocomprise a PVDF homopolymer.

The fluoropolymer may comprise a high molecular weight PVDF having aweight average molecular weight of at least 50,000 g/mol, such as atleast 100,000 g/mol, and may range from 50,000 g/mol to 1,500,000 g/mol,such as 100,000 g/mol to 1,000,000 g/mol. PVDF is commerciallyavailable, e.g., from Arkema under the trademark KYNAR and from InnerMongolia 3F Wanhao Fluorochemical Co., Ltd.

The fluoropolymer may comprise a nanoparticle. As used herein, the term“nanoparticle” refers to particles having a particle size of less than1,000 nm. The fluoropolymer may have a particle size of at least 50 nm,such as at least 100 nm, such as at least 250 nm, such as at least 300nm, and may be no more than 900 nm, such as no more than 600 nm, such asno more than 450 nm, such as no more than 400 nm, such as no more than300 nm, such as no more than 200 nm. The fluoropolymer nanoparticles mayhave a particle size of 50 nm to 900 nm, such as 100 nm to 600 nm, suchas 250 nm to 450 nm, such as 300 nm to 400 nm, such as 100 nm to 400 nm,such as 100 nm to 300 nm, such as 100 nm to 200 nm. As used herein, theterm “particle size” refers to average diameter of the fluoropolymerparticles. The particle size referred to in the present disclosure wasdetermined by the following procedure: A sample was prepared bydispersing the fluoropolymer onto a segment of carbon tape that wasattached to an aluminum scanning electron microscope (SEM) stub. Excessparticles were blown off the carbon tape with compressed air. The samplewas then sputter coated with Au/Pd for 20 seconds and was then analyzedin a Quanta 250 FEG SEM (field emission gun scanning electronmicroscope) under high vacuum. The accelerating voltage was set to 20.00kV and the spot size was set to 3.0. Images were collected from threedifferent areas on the prepared sample, and ImageJ software was used tomeasure the diameter of 10 fluoropolymer particles from each area for atotal of 30 particle size measurements that were averaged together todetermine the average particle size.

The fluoropolymer may be present in in the binder in amounts of 40% to100% by weight, such as 40% to 96% by weight, such as 50% to 90% byweight, based on the total weight of the binder solids.

The liquid medium of the slurry composition may comprise an organicmedium. As used herein, the term “organic medium” refers to a liquidmedium comprising less than 50% by weight water, based on the totalweight of the organic medium. Such organic mediums may comprise lessthan 40% by weight water, or less than 30% by weight water, or less than20% by weight water, or less than 10% by weight water, or less than 5%by weight water, or less than 1% by weight water, or less than 0.1% byweight water, based on the total weight of the organic medium, or may befree of water. Organic solvent(s) comprise more than 50% by weight ofthe organic medium, such as at least 70% by weight, such as at least 80%by weight, such as at least 90% by weight, such as at least 95% byweight, such as at least 99% by weight, such as at least 99.9% byweight, such as 100% by weight, based on the total weight of the organicmedium. The organic solvent(s) may comprise 50.1% to 100% by weight,such as 70% to 100% by weight, such as 80% to 100% by weight, such as90% to 100% by weight, such as 95% to 100% by weight, such as 99% to100% by weight, such as 99.9% to 100% by weight, based on the totalweight of the organic medium.

The organic medium may comprise, consist essentially of, or consist of,for example, ketones such as methyl ethyl ketone, cyclohexanone andisophorone, ethers such as the C₁ to C₄ alkyl ethers of ethylene andpropylene glycol, butyl pyrrolidone, trialkyl phosphate,1,2,3-triacetoxypropane, 3-methoxy-N,N-dimethylpropanamide, ethylacetoacetate, gamma-butyrolactone, propylene glycol methyl ether,propylene carbonate, dimethyl adipate, propylene glycol methyl etheracetate, dibasic ester (DBE), dibasic ester 5 (DBE-5),4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), propylene glycoldiacetate, dimethyl phthalate, methyl isoamyl ketone, ethyl propionate,1-ethoxy-2-propanol, dipropylene glycol dimethyl ether, saturated andunsaturated linear and cyclic ketones (commercially available as amixture thereof as Eastman™ C-11 Ketone from Eastman Chemical Company),diisobutyl ketone, acetate esters (commercially available as Exxate™1000 from Hallstar), tripropylene glycol methyl ether, diethylene glycolethyl ether acetate, or combinations thereof. The trialkyl phosphate maycomprise, for example, trimethylphosphate, triethylphosphate,tripropylphosphate, tributylphosphate, or the like.

As discussed above, the organic medium has an evaporation rate less than10 g/min m², at the dissolution temperature of the fluoropolymerdispersed in the organic medium. Evaporation rates may be measured usingASTM D3539 (1996). According to the present invention, the dissolutiontemperature of the fluoropolymer dispersed in the organic medium may bedetermined by measuring complex viscosity of the mixture as a functionof temperature. This technique may be applied to fluoropolymers (inaddition to other types of polymer) mixed in an organic medium where thetotal mass of non-volatile solids content of such mixtures is from 44%to 46%, such as 45% of the total mass of the mixture. Complex viscositymay be measured with an Anton-Paar MCR301 rheometer using a50-millimeter cone and temperature-controlled plate. The complexviscosity of fluoropolymer mixtures is measured over a temperature rangefrom 35° C. to at least 75° C. with a temperature ramp rate of 10° C.per minute, an oscillatory frequency of 1 Hz, and a stress amplitudelimit of 90 Pa. The dissolution of fluoropolymer in the organic mediumis indicated by a sharp increase in the complex viscosity as temperatureincreased. The dissolution temperature is defined as the temperature atwhich the rate of change in viscosity with ramping temperature ishighest and is calculated by determining the temperature at which thefirst derivative with respect to temperature of the Log₁₀ of the complexviscosity reaches a maximum. FIG. 1 is a graph illustrating the firstderivative of Log₁₀ viscosity versus temperature, wherein the peakmaximum is used to determine the dissolution temperature of thefluoropolymer polyvinylidene fluoride (PVDF T-1 from Inner Mongolia 3FWanhao Fluorochemical Co. Ltd.) dispersed in the organic medium1,2,3-triacetoxypropane (triacetin) from the abscissa. The table belowillustrates dissolution temperatures determined according to this methodusing PVDF T-1 from Inner Mongolia 3F Wanhao Fluorochemical Co. Ltd.(PVDF T-1 has a particle size of about 330 to 380 nm and a weightaverage molecular weight of about 130,000 to 160,000 g/mol), in varioussolvents or solvent mixtures as listed.

Evaporation Solvent Cosolvent rate at % mass of % mass of PVDF %Dissolution Dissolution organic organic mass of Temp Temp Solvent mediumCosolvent medium mixture (° C.) (mg/min m²) N-butylpyrrolidone 100 — —45 48 — gamma- 100 — — 45 51 9.31 butyrolactone Isophorone 100 — — 45 7216.59 Triacetin 100 — — 45 76 0.69 Ethyl Acetoacetate 100 — — 45 7637.76 Triethylphosphate 80 Ethyl 20 45 46 — AcetoacetateTriethylphosphate 80 Dowanol ™ 20 45 58 — PM¹ ¹Propylene glycol methylether commercially available from The Dow Chemical Company.

The dissolution temperature of the fluoropolymer dispersed in theorganic medium may be less than 77° C., such as less than 70° C., suchas less than 65° C., such as less than 60° C., such as less than 55° C.,such as less than 50° C. The dissolution temperature of thefluoropolymer dispersed in the organic medium may range from 30° C. to77° C., such as from 30° C. to 70° C., such as 30° C. to 65° C., such as30° C. to 60° C., such as 30° C. to 55° C., such as 30° C. to 50° C. Thedissolution temperature may be measured according to the methoddiscussed above.

The organic medium may comprise, for example, butyl pyrrolidone,trialkyl phosphate, 1,2,3-triacetoxypropane,3-methoxy-N,N-dimethylpropanamide, ethyl acetoacetate,gamma-butyrolactone, propylene glycol methyl ether, cyclohexanone,propylene carbonate, dimethyl adipate, propylene glycol methyl etheracetate, dibasic ester (DBE), dibasic ester 5 (DBE-5),4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), propylene glycoldiacetate, dimethyl phthalate, methyl isoamyl ketone, ethyl propionate,1-ethoxy-2-propanol, dipropylene glycol dimethyl ether, saturated andunsaturated linear and cyclic ketones (commercially available as amixture thereof as Eastman™ C-11 Ketone from Eastman Chemical Company),diisobutyl ketone, acetate esters (commercially available as Exxate™1000 from Hallstar), tripropylene glycol methyl ether, diethylene glycolethyl ether acetate, or combinations thereof. The trialkyl phosphate maycomprise, for example, trimethylphosphate, triethylphosphate,tripropylphosphate, tributylphosphate, or the like.

The organic medium may consist essentially of or consist of, forexample, butyl pyrrolidone, trialkyl phosphate, 1,2,3-triacetoxypropane,3-methoxy-N,N-dimethylpropanamide, ethyl acetoacetate,gamma-butyrolactone, cyclohexanone, propylene carbonate, dimethyladipate, propylene glycol methyl ether acetate, dibasic ester (DBE),dibasic ester 5 (DBE-5), 4-hydroxy-4-methyl-2-pentanone (diacetonealcohol), propylene glycol diacetate, dimethyl phthalate, methyl isoamylketone, ethyl propionate, 1-ethoxy-2-propanol, saturated and unsaturatedlinear and cyclic ketones (commercially available as a mixture thereofas Eastman™ C-11 Ketone from Eastman Chemical Company), diisobutylketone, acetate esters (commercially available as Exxate™ 1000 fromHallstar), diethylene glycol ethyl ether acetate, or combinationsthereof.

The organic medium may comprise a primary solvent and a co-solvent thatform a homogenous continuous phase with the fluoropolymer as thedispersed phase. The primary solvent and co-solvent and relevant amountsthereof may be selected to provide a dispersion of the fluoropolymer inthe organic medium at room temperature, i.e., about 23° C. Both theprimary solvent and co-solvent may comprise organic solvent(s). Thefluoropolymer may be soluble in the primary solvent at room temperatureif used alone but use of the co-solvent with the primary solvent mayallow for the fluoropolymer to be stably dispersed in the organicmedium. The primary solvent may comprise, consist essentially of, orconsist of, for example, butyl pyrrolidone, a trialkylphosphate,3-methoxy-N,N-dimethylpropanamide, 1,2,3-triacetoxypropane, orcombinations thereof. The co-solvent may comprise, consist essentiallyof, or consist of, for example, ethyl acetoacetate, gamma-butyrolactone,and/or glycol ethers such as propylene glycol methyl ether, dipropyleneglycol methyl ether, propylene glycol monopropyl ether, diethyleneglycol monobutyl ether, ethylene glycol monohexyl ether, and the like.The primary solvent may be present in an amount of at least 50% byweight, such as at least 65% by weight, such as at least 75 by weight,and may be present in an amount of no more than 99% by weight, such asno more than 90% by weight, such as no more than 85% by weight, based onthe total weight of the organic medium. The primary solvent may bepresent in an amount of 50% to 99% by weight, such as 65% to 90% byweight, such as 75% to 85% by weight, based on the total weight of theorganic medium. The co-solvent may be present in an amount of at least1% by weight, such as at least 10% by weight, such as at least 15% byweight, and may be present in an amount of no more than 50% by weight,such as no more than 35% by weight, such as no more than 25% by weight.The co-solvent may be present in an amount of 1% to 50% by weight, suchas 10% to 35% by weight, such as 15% to 25% by weight, based on thetotal weight of the organic medium.

The organic medium may also have an evaporation rate greater than 80g/min m², at 180° C., such as greater than 90 g/min m², at 180° C., suchas greater than 100 g/min m², at 180° C.

The liquid medium may comprise an aqueous medium. As used herein, theterm “aqueous medium” refers to a liquid medium comprising at least 50%by weight water, based on the total weight of the organic medium. Suchaqueous mediums may comprise less than 40% by weight organic solvent, orless than 30% by weight organic solvent, or less than 20% by weightorganic solvent, or less than 10% by weight organic solvent, or lessthan 5% by weight organic solvent, or less than 1% by weight organicsolvent, or less than 0.1% by weight organic solvent, based on the totalweight of the aqueous medium. Water may comprise more than 50% by weightof the aqueous medium, such as at least 60% by weight, such as at least70% by weight, such as at least 80% by weight, such as at least 90% byweight, such as at least 95% by weight, such as at least 99% by weight,such as at least 99.9% by weight, such as 100% by weight, based on thetotal weight of the aqueous medium. Water may comprise 50.1% to 100% byweight, such as 70% to 100% by weight, such as 80% to 100% by weight,such as 90% to 100% by weight, such as 95% to 100% by weight, such as99% to 100% by weight, such as 99.9% to 100% by weight, based on thetotal weight of the aqueous medium.

The liquid medium may be present in an amount of at least 10% by weight,such as at least 15% by weight, such as at least 20% by weight, such asat least 30% by weight, such as at least 35% by weight, such as at least40% by weight, and may be present in an amount of no more than 80% byweight, such as no more than 70% by weight, such as no more than 60% byweight, such as no more than 50% by weight, such as no more than 45% byweight, such as no more than 45% by weight, such as no more than 40% byweight, such as no more than 35% by weight, such as no more than 29% byweight, such as no more than 25% by weight, based on the total weight ofthe slurry composition. The liquid medium may be present in an amount ofsuch as 20% to 80% by weight, 10% to 70% by weight, such as 30% to 70%by weight, such as 35% to 60% by weight, such as 40% to 50% by weight,15% to 60% by weight, 15% to 50% by weight, 15% to 45% by weight, 15% to40% by weight, 15% to 35% by weight, 15% to 29% by weight, 15% to 25% byweight, based on the total weight of the slurry composition.

The slurry composition may be substantially free, essentially free, orcompletely free of N-Methyl-2-pyrrolidone (NMP). As used herein, theslurry composition is “substantially free” of NMP if NMP is present, ifat all, in an amount of less than 5% by weight, based on the totalweight of the slurry composition. As used herein, the slurry compositionis “essentially free” of NMP if NMP is present, if at all, in an amountof less than 0.3% by weight, based on the total weight of the slurrycomposition. As used herein, the slurry composition is “completely free”of NMP if NMP is not present in the slurry composition, i.e., 0.0% byweight, based on the total weight of the slurry composition.

The slurry composition may be substantially free, essentially free, orcompletely free of ketones such as methyl ethyl ketone, cyclohexanone,isophorone, acetophenone.

The slurry composition may be substantially free, essentially free, orcompletely free of ethers such as the C₁ to C₄ alkyl ethers of ethyleneor propylene glycol.

The slurry composition further comprises an adhesion promoter. Theadhesion promoter may comprise a polyvinylidene fluoride copolymerdifferent than the fluoropolymer described above, an acid-functionalpolyolefin, or a thermoplastic material.

The polyvinylidene fluoride copolymer adhesion promoter comprisesconstitutional units comprising the residue of vinylidene fluoride andat least one of (i) a (meth)acrylic acid; and/or (ii) a hydroxyalkyl(meth)acrylate. The (meth)acrylic acid may comprise acrylic acid,methacrylic acid, or combinations thereof. The hydroxyalkyl(meth)acrylate may comprise a C₁ to C₅ hydroxyalkyl (meth)acrylate, suchas, for example, hydroxyethyl (meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl (meth)acrylate, or combinations thereof.The polyvinylidene fluoride copolymer adhesion promoter comprises atleast 50% by moles of constitutional units comprising the residue ofvinylidene fluoride, such as at least 70% by moles, such as at least 80%by moles and no more than 99% by moles, such as no more than 98% bymoles, such as no more than 95% by moles, based on the total molarcontent of the polyvinylidene fluoride copolymer adhesion promoter. Thepolyvinylidene fluoride copolymer adhesion promoter comprises 50% to 99%by moles of constitutional units comprising the residue of vinylidenefluoride, such as 70% to 98% by moles, such as 80% to 95% by moles,based on the total molar content of the polyvinylidene fluoridecopolymer adhesion promoter. The polyvinylidene fluoride copolymeradhesion promoter may comprise at least 0.01% by moles of constitutionalunits comprising the residue of the (meth)acrylic acid, such as at least0.02% by moles, such as at least 0.03% by moles, and may comprise nomore than 10% by moles, such as no more than 5% by moles, such as nomore than 2% by moles, based on the total molar content of thepolyvinylidene fluoride copolymer adhesion promoter. The polyvinylidenefluoride copolymer adhesion promoter may comprise 0.01% to 10% by molesof constitutional units comprising the residue of the (meth)acrylicacid, such as 0.02% to 5% by moles, such as 0.03% to 2% by moles, basedon the total molar content of the polyvinylidene fluoride copolymeradhesion promoter. The polyvinylidene fluoride copolymer adhesionpromoter may comprise at least 0.01% by moles of constitutional unitscomprising the residue of the hydroxyalkyl (meth)acrylate, such as atleast 0.02% by moles, such as at least 0.03% by moles, and may compriseno more than 10% by moles, such as no more than 5% by moles, such as nomore than 2% by moles, based on the total molar content of thepolyvinylidene fluoride copolymer adhesion promoter. The polyvinylidenefluoride copolymer adhesion promoter may comprise 0.01% to 10% by molesof constitutional units comprising the residue of the hydroxyalkyl(meth)acrylate, such as 0.02% to 5% by moles, such as 0.03% to 2% bymoles, based on the total molar content of the polyvinylidene fluoridecopolymer adhesion promoter. A commercially available example of such anaddition polymer includes SOLEF 5130, available from Solvay. Unlike thefluoropolymer discussed above, the polyvinylidene fluoride copolymer maybe dispersed or solubilized in the organic medium of the slurrycomposition.

The acid-functional polyolefin adhesion promoter comprises anethylene-(meth)acrylic acid copolymer, such as an ethylene-acrylic acidcopolymer or an ethylene-methacrylic acid copolymer. Theethylene-acrylic acid copolymer may comprise constitutional unitscomprising 10% to 50% by weight acrylic acid, such as 15% to 30% byweight, such as 17% to 25% by weight, such as about 20% by weight, basedon the total weight of the ethylene-acrylic acid copolymer, and 50% to90% by weight ethylene, such as 70% to 85% by weight, such as 75% to 83%by weight, such as about 80% by weight, based on the total weight of theethylene-acrylic acid copolymer. A commercially available example ofsuch an addition polymer includes PRIMACOR 5980i, available from the DowChemical Company.

The adhesion promoter may be present in the slurry composition in anamount of 10% to 60% by weight, such as 20% to 60% by weight, such as30% to 60% by weight, such as 10% to 50% by weight, such as 15% to 40%by weight, such as 20% to 30% by weight, such as 35% to 35% by weight,based on the total weight of the binder solids (including the adhesionpromoter).

The slurry composition may optionally further comprise a dispersant. Thedispersant may assist in dispersing the fluoropolymer, and/or, ifpresent, the electrically conductive agent and/or the electrochemicallyactive material in the liquid medium. When present, the dispersant maybe a component of the slurry composition binder. The dispersant maycomprise at least one phase that is compatible with the fluoropolymerand/or other components of the slurry composition, such as theelectrically conductive agent or electrochemically active material, ifpresent, and may further comprise at least one phase that is compatiblewith the liquid medium. The slurry composition may comprise one, two,three, four or more different dispersants, and each dispersant mayassist in dispersing a different component of the slurry composition.The dispersant may comprise any material having phases compatible withboth the fluoropolymer and/or, if present, the electrically conductiveagent or electrochemically active material, and the liquid medium. Asused herein, the term “compatible” means the ability of a material toform a blend with other materials that is and will remain substantiallyhomogenous over time. The fluoropolymer and dispersant may not be boundby a covalent bond. For example, the dispersant may comprise a polymercomprising such phases. The polymer may be in the form of a blockpolymer, a random polymer, or a gradient polymer, wherein the phases ofpresent in the different blocks of the polymer, are randomly includedthroughout the polymer, or are progressively more or less denselypresent along the polymer backbone, respectively. The dispersant maycomprise any suitable polymer to serve this purpose. For example, thepolymer may comprise addition polymers produced by polymerizingethylenically unsaturated monomers, polyepoxide polymers, polyamidepolymers, polyurethane polymers, polyurea polymers, polyether polymers,polyacid polymers, and polyester polymers, among others. The dispersantmay also serve as an additional component of the binder of the slurrycomposition.

The dispersant may comprise functional groups. The functional groups maycomprise, for example, active hydrogen functional groups, heterocyclicgroups, and combinations thereof. As used herein, the term “activehydrogen functional groups” refers to those groups that are reactivewith isocyanates as determined by the Zerewitinoff test described in theJOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Vol. 49, page 3181 (1927), andinclude, for example, hydroxyl groups, primary or secondary aminogroups, carboxylic acid groups, and thiol groups. As used herein, theterm “heterocyclic group” refers to a cyclic group containing at leasttwo different elements in its ring such as a cyclic moiety having atleast one atom in addition to carbon in the ring structure, such as, forexample, oxygen, nitrogen or sulfur. Non-limiting examples ofheterocylic groups include epoxides, lactams and lactones. In addition,when epoxide functional groups are present on the addition polymer, theepoxide functional groups on the dispersant may be post-reacted with abeta-hydroxy functional acid. Non-limiting examples of beta-hydroxyfunctional acids include citric acid, tartaric acid, and/or an aromaticacid, such as 3-hydroxy-2-naphthoic acid. The ring opening reaction ofthe epoxide functional group will yield hydroxyl functional groups onthe dispersant.

When acid functional groups are present, the dispersant may have atheoretical acid equivalent weight of at least 350 g/acid equivalent,such as at least 878 g/acid equivalent, such as at least 1,757 g/acidequivalent, and may be no more than 17,570 g/acid equivalent, such as nomore than 12,000 g/acid equivalent, such as no more than 7,000 g/acidequivalent. The dispersant may have a theoretical acid equivalent weightof 350 to 17,570 g/acid equivalent, such as 878 to 12,000 g/acidequivalent, such as 1,757 to 7,000 g/acid equivalent.

As mentioned above, the dispersant may comprise an addition polymer. Theaddition polymer may be derived from, and comprise constitutional unitscomprising the residue of, one or more alpha, beta-ethylenicallyunsaturated monomers, such as those discussed below, and may be preparedby polymerizing a reaction mixture of such monomers. The mixture ofmonomers may comprise one or more active hydrogen group-containingethylenically unsaturated monomers. The reaction mixture may alsocomprise ethylenically unsaturated monomers comprising a heterocyclicgroup. As used herein, an ethylenically unsaturated monomer comprising aheterocyclic group refers to a monomer having at least one alpha, betaethylenic unsaturated group and at least cyclic moiety having at leastone atom in addition to carbon in the ring structure, such as, forexample, oxygen, nitrogen or sulfur. Non-limiting examples ofethylenically unsaturated monomers comprising a heterocyclic groupinclude epoxy functional ethylenically unsaturated monomers, vinylpyrrolidone and vinyl caprolactam, among others. The reaction mixturemay additionally comprise other ethylenically unsaturated monomers suchas alkyl esters of (meth)acrylic acid and others described below.

The addition polymer may comprise a (meth)acrylic polymer that comprisesconstitutional units comprising the residue of one or more (meth)acrylicmonomers. The (meth)acrylic polymer may be prepared by polymerizing areaction mixture of alpha, beta-ethylenically unsaturated monomers thatcomprise one or more (meth)acrylic monomers and optionally otherethylenically unsaturated monomers. As used herein, the term“(meth)acrylic monomer” refers to acrylic acid, methacrylic acid, andmonomers derived therefrom, including alkyl esters of acrylic acid andmethacrylic acid, and the like. As used herein, the term “(meth)acrylicpolymer” refers to a polymer derived from or comprising constitutionalunits comprising the residue of one or more (meth)acrylic monomers. Themixture of monomers may comprise one or more active hydrogengroup-containing (meth)acrylic monomers, ethylenically unsaturatedmonomers comprising a heterocyclic group, and other ethylenicallyunsaturated monomers. The (meth)acrylic polymer may also be preparedwith an epoxy functional ethylenically unsaturated monomer such asglycidyl methacrylate in the reaction mixture, and epoxy functionalgroups on the resulting polymer may be post-reacted with a beta-hydroxyfunctional acid such as citric acid, tartaric acid, and/or3-hydroxy-2-naphthoic acid to yield hydroxyl functional groups on the(meth)acrylic polymer.

The addition polymer may comprise constitutional units comprising theresidue of an alpha, beta-ethylenically unsaturated carboxylic acid.Non-limiting examples of alpha, beta-ethylenically unsaturatedcarboxylic acids include those containing up to 10 carbon atoms such asacrylic acid and methacrylic acid. Non-limiting examples of otherunsaturated acids are alpha, beta-ethylenically unsaturated dicarboxylicacids such as maleic acid or its anhydride, fumaric acid and itaconicacid. Also, the half esters of these dicarboxylic acids may be employed.The constitutional units comprising the residue of the alpha,beta-ethylenically unsaturated carboxylic acids may comprise at least 1%by weight, such as at least 2% by weight, such as at least 5% by weight,and may be no more than 50% by weight, such as no more than 20% byweight, such as no more than 10% by weight, such as no more than 5% byweight, based on the total weight of the addition polymer. Theconstitutional units comprising the residue of the alpha,beta-ethylenically unsaturated carboxylic acids may comprise 1% to 50%by weight, 2% to 50% by weight, such as 2% to 20% by weight, such as 2%to 10% by weight, such as 2% to 5% by weight, such as 1% to 5% byweight, based on the total weight of the addition polymer. The additionpolymer may be derived from a reaction mixture comprising the alpha,beta-ethylenically unsaturated carboxylic acids in an amount of 1% to50% by weight, 2% to 50% by weight, such as 2% to 20% by weight, such as2% to 10% by weight, such as 2% to 5% by weight, such as 1% to 5% byweight, based on the total weight of polymerizable monomers used in thereaction mixture. The inclusion of constitutional units comprising theresidue of an alpha, beta-ethylenically unsaturated carboxylic acids inthe dispersant results in a dispersant comprising at least onecarboxylic acid group which may assist in providing stability to thedispersion.

The addition polymer may comprise constitutional units comprising theresidue of an alkyl esters of (meth)acrylic acid containing from 1 to 3carbon atoms in the alkyl group. Non-limiting examples of alkyl estersof (meth)acrylic acid containing from 1 to 3 carbon atoms in the alkylgroup include methyl (meth)acrylate and ethyl (meth)acrylate. Theconstitutional units comprising the residue of the alkyl esters of(meth)acrylic acid containing from 1 to 3 carbon atoms in the alkylgroup may comprise at least 20% by weight, such as at least 30% byweight, such as at least 40% by weight, such as at least 45% by weight,such as at least 50% by weight, and may be no more than 98% by weight,such as no more than 96% by weight, such as no more than 90% by weight,such as no more than 80% by weight, such as no more than 75% by weight,based on the total weight of the addition polymer. The constitutionalunits comprising the residue of the alkyl esters of (meth)acrylic acidcontaining from 1 to 3 carbon atoms in the alkyl group may comprise 20%to 98% by weight, such as 30% to 96% by weight, such as 30% to 90% byweight, 40% to 90% by weight, such as 40% to 80% by weight, such as 45%to 75% by weight, based on the total weight of the addition polymer. Theaddition polymer may be derived from a reaction mixture comprising thealkyl esters of (meth)acrylic acid containing from 1 to 3 carbon atomsin the alkyl group in an amount of 20% to 98% by weight, such as 30% to96% by weight, such as 30% to 90% by weight, 40% to 90% by weight, suchas 40% to 80% by weight, such as 45% to 75% by weight, based on thetotal weight of polymerizable monomers used in the reaction mixture.

The addition polymer may comprise constitutional units comprising theresidue of an alkyl esters of (meth)acrylic acid containing from 4 to 18carbon atoms in the alkyl group. Non-limiting examples of alkyl estersof (meth)acrylic acid containing from 4 to 18 carbon atoms in the alkylgroup include butyl (meth)acrylate, hexyl (meth)acrylate, octyl(meth)acrylate, isodecyl (meth)acrylate, stearyl (meth)acrylate,2-ethylhexyl (meth)acrylate, decyl (meth)acrylate and dodecyl(meth)acrylate. The constitutional units comprising the residue of thealkyl esters of (meth)acrylic acid containing from 4 to 18 carbon atomsin the alkyl group may comprise at least 2% by weight, such as at least5% by weight, such as at least 10% by weight, such as at least 15% byweight, such as at least 20% by weight, and may be no more than 70% byweight, such as no more than 60% by weight, such as no more than 50% byweight, such as no more than 40% by weight, such as no more than 35% byweight, based on the total weight of the addition polymer. Theconstitutional units comprising the residue of the alkyl esters of(meth)acrylic acid containing from 4 to 18 carbon atoms in the alkylgroup may comprise 2% to 70% by weight, such as 2% to 60% by weight,such as 5% to 50% by weight, 10% to 40% by weight, such as 15% to 35% byweight, based on the total weight of the addition polymer. The additionpolymer may be derived from a reaction mixture comprising the alkylesters of (meth)acrylic acid containing from 4 to 18 carbon atoms in thealkyl group in an amount of 2% to 70% by weight, such as 2% to 60% byweight, such as 5% to 50% by weight, 10% to 40% by weight, such as 15%to 35% by weight, based on the total weight of polymerizable monomersused in the reaction mixture.

The addition polymer may comprise constitutional units comprising theresidue of a hydroxyalkyl ester. Non-limiting examples of hydroxyalkylesters include hydroxyethyl (meth)acrylate and hydroxypropyl(meth)acrylate. The constitutional units comprising the residue of thehydroxyalkyl ester may comprise at least 0.5% by weight, such as atleast 1% by weight, such as at least 2% by weight, and may be no morethan 30% by weight, such as no more than 20% by weight, such as no morethan 10% by weight, such as no more than 5% by weight, based on thetotal weight of the addition polymer. The constitutional unitscomprising the residue of the hydroxyalkyl ester may comprise 0.5% to30% by weight, such as 1% to 20% by weight, such as 2% to 20% by weight,2% to 10% by weight, such as 2% to 5% by weight, based on the totalweight of the addition polymer. The addition polymer may be derived froma reaction mixture comprising the hydroxyalkyl ester in an amount of0.5% to 30% by weight, such as 1% to 20% by weight, such as 2% to 20% byweight, 2% to 10% by weight, such as 2% to 5% by weight, based on thetotal weight of polymerizable monomers used in the reaction mixture. Theinclusion of constitutional units comprising the residue of ahydroxyalkyl ester in the dispersant results in a dispersant comprisingat least one hydroxyl group (although hydroxyl groups may be included byother methods). Hydroxyl groups resulting from inclusion of thehydroxyalkyl esters (or incorporated by other means) may react with aseparately added crosslinking agent that comprises functional groupsreactive with hydroxyl groups such as, for example, an aminoplast,phenolplast, polyepoxides and blocked polyisocyanates, or withN-alkoxymethyl amide groups or blocked isocyanato groups present in theaddition polymer when self-crosslinking monomers that have groups thatare reactive with the hydroxyl groups are incorporated into the additionpolymer.

The addition polymer may comprise constitutional units comprising theresidue of an ethylenically unsaturated monomer comprising aheterocyclic group. Non-limiting examples of ethylenically unsaturatedmonomers comprising a heterocyclic group include epoxy functionalethylenically unsaturated monomers, such as glycidyl (meth)acrylate,vinyl pyrrolidone and vinyl caprolactam, among others. Theconstitutional units comprising the residue of the ethylenicallyunsaturated monomers comprising a heterocyclic group may comprise atleast 0.5% by weight, such as at least 1% by weight, such as at least 5%by weight, such as at least 8% by weight, and may be no more than 99% byweight, such as no more than 50% by weight, such as no more than 40% byweight, such as no more than 30% by weight, such as no more than 27% byweight, based on the total weight of the addition polymer. Theconstitutional units comprising the residue of the ethylenicallyunsaturated monomers comprising a heterocyclic group may comprise 0.5%to 99% by weight, such as 0.5% to 50% by weight, such as 1% to 40% byweight, such as 5% to 30% by weight, 8% to 27% by weight, based on thetotal weight of the addition polymer. The addition polymer may bederived from a reaction mixture comprising the ethylenically unsaturatedmonomers comprising a heterocyclic group in an amount of 0.5% to 50% byweight, such as 1% to 40% by weight, such as 5% to 30% by weight, 8% to27% by weight, based on the total weight of polymerizable monomers usedin the reaction mixture.

As noted above, the addition polymer may comprise constitutional unitscomprising the residue of a self-crosslinking monomer, and the additionpolymer may comprise a self-crosslinking addition polymer. As usedherein, the term “self-crosslinking monomer” refers to monomers thatincorporate functional groups that may react with other functionalgroups present on the dispersant to a crosslink between the dispersantor more than one dispersant. Non-limiting examples of self-crosslinkingmonomers include N-alkoxymethyl (meth)acrylamide monomers such asN-butoxymethyl (meth)acrylamide and N-isopropoxymethyl (meth)acrylamide,as well as self-crosslinking monomers containing blocked isocyanategroups, such as isocyanatoethyl (meth)acrylate in which the isocyanatogroup is reacted (“blocked”) with a compound that unblocks at curingtemperature. Examples of suitable blocking agents includeepsilon-caprolactone and methylethyl ketoxime. The constitutional unitscomprising the residue of the self-crosslinking monomer may comprise atleast 0.5% by weight, such as at least 1% by weight, such as at least 2%by weight, and may be no more than 30% by weight, such as no more than20% by weight, such as no more than 10% by weight, such as no more than5% by weight, based on the total weight of the addition polymer. Theconstitutional units comprising the residue of the self-crosslinkingmonomer may comprise 0.5% to 30% by weight, such as 1% to 20% by weight,such as 2% to 20% by weight, 2% to 10% by weight, such as 2% to 5% byweight, based on the total weight of the addition polymer. The additionpolymer may be derived from a reaction mixture comprising theself-crosslinking monomer in an amount of 0.5% to 30% by weight, such as1% to 20% by weight, such as 2% to 20% by weight, 2% to 10% by weight,such as 2% to 5% by weight, based on the total weight of polymerizablemonomers used in the reaction mixture.

The addition polymer may comprise constitutional units comprising theresidue of other alpha, beta-ethylenically unsaturated monomers.Non-limiting examples of other alpha, beta-ethylenically unsaturatedmonomers include vinyl aromatic compounds such as styrene, alpha-methylstyrene, alpha-chlorostyrene and vinyl toluene; organic nitriles such asacrylonitrile and methacrylonitrile; allyl monomers such as allylchloride and allyl cyanide; monomeric dienes such as 1,3-butadiene and2-methyl-1,3-butadiene; and acetoacetoxyalkyl (meth)acrylates such asacetoacetoxyethyl methacrylate (AAEM) (which may be self-crosslinking).The constitutional units comprising the residue of the other alpha,beta-ethylenically unsaturated monomers may comprise at least 0.5% byweight, such as at least 1% by weight, such as at least 2% by weight,and may be no more than 30% by weight, such as no more than 20% byweight, such as no more than 10% by weight, such as no more than 5% byweight, based on the total weight of the addition polymer. Theconstitutional units comprising the residue of the other alpha,beta-ethylenically unsaturated monomers may comprise 0.5% to 30% byweight, such as 1% to 20% by weight, such as 2% to 20% by weight, 2% to10% by weight, such as 2% to 5% by weight, based on the total weight ofthe addition polymer. The addition polymer may be derived from areaction mixture comprising the other alpha, beta-ethylenicallyunsaturated monomers in an amount of 0.5% to 30% by weight, such as 1%to 20% by weight, such as 2% to 20% by weight, 2% to 10% by weight, suchas 2% to 5% by weight, based on the total weight of polymerizablemonomers used in the reaction mixture.

The monomers and relative amounts may be selected such that theresulting addition polymer has a Tg of 100° C. or less, typically from−50° C. to +70° C., such as −50° C. to 0° C. A lower Tg that is below 0°C. may be desirable to ensure acceptable battery performance at lowtemperature.

The addition polymers may be prepared by conventional free radicalinitiated solution polymerization techniques in which the polymerizablemonomers are dissolved in a second organic medium comprising a solventor a mixture of solvents and polymerized in the presence of a freeradical initiator until conversion is complete. The second organicmedium used to prepare the addition polymer may be the same as theorganic medium present in the slurry composition such that thecomposition of the organic medium is unchanged by addition of theaddition polymer solution. For example, the second organic medium maycomprise the same primary solvent(s) and co-solvent(s) in the sameratios as the organic medium of the slurry composition. Alternatively,the second organic medium used to prepare the addition polymer may bedifferent and distinct from the organic medium of the slurrycomposition. The second organic medium used to produce the additionpolymer may comprise any suitable organic solvent or mixture ofsolvents, including those discussed above with respect to the organicmedium, such as, for example, triethylphosphate.

Examples of free radical initiators are those which are soluble in themixture of monomers such as azobisisobutyronitrile, azobis(alpha,gamma-methylvaleronitrile), tertiary-butyl perbenzoate, tertiary-butylperacetate, benzoyl peroxide, ditertiary-butyl peroxide and tertiaryamyl peroxy 2-ethylhexyl carbonate.

Optionally, a chain transfer agent which is soluble in the mixture ofmonomers such as alkyl mercaptans, for example, tertiary-dodecylmercaptan; ketones such as methyl ethyl ketone, chlorohydrocarbons suchas chloroform can be used. A chain transfer agent provides control overthe molecular weight to give products having required viscosity forvarious coating applications. Tertiary-dodecyl mercaptan is preferredbecause it results in high conversion of monomer to polymeric product.

To prepare the addition polymer, the solvent may be first heated toreflux and the mixture of polymerizable monomers containing the freeradical initiator may be added slowly to the refluxing solvent. Thereaction mixture is then held at polymerizing temperatures so as toreduce the free monomer content, such as to below 1.0 percent andusually below 0.5 percent, based on the total weight of the mixture ofpolymerizable monomers.

For use in the slurry composition of the invention, the dispersantsprepared as described above usually have a weight average molecularweight of about 5000 to 500,000 g/mol, such as 10,000 to 100,000 g/mol,and 25,000 to 50,000 g/mol.

The dispersant may be present in the binder in amounts of 2% to 20% byweight, such as 5% to 15% by weight, based on the total weight of thebinder solids.

As noted above, the slurry composition may optionally further comprise aseparately added crosslinking agent for reaction with the dispersant.The crosslinking agent should be soluble or dispersible in the liquidmedium and be reactive with active hydrogen groups of the dispersant,such as the carboxylic acid groups and the hydroxyl groups, if present.Non-limiting examples of suitable crosslinking agents include aminoplastresins, blocked polyisocyanates and polyepoxides.

Examples of aminoplast resins for use as a crossslinking agent are thosewhich are formed by reacting a triazine such as melamine orbenzoguanamine with formaldehyde. These reaction products containreactive N-methylol groups. Usually, these reactive groups areetherified with methanol, ethanol, butanol including mixtures thereof tomoderate their reactivity. For the chemistry preparation and use ofaminoplast resins, see “The Chemistry and Applications of AminoCrosslinking Agents or Aminoplast”, Vol. V, Part II, page 21 ff., editedby Dr. Oldring; John Wiley & Sons/Cita Technology Limited, London, 1998.These resins are commercially available under the trademark MAPRENAL®such as MAPRENAL MF980 and under the trademark CYMEL® such as CYMEL 303and CYMEL 1128, available from Cytec Industries.

Blocked polyisocyanate crosslinking agents are typically diisocyanatessuch as toluene diisocyanate, 1,6-hexamethylene diisocyanate andisophorone diisocyanate including isocyanato dimers and trimers thereofin which the isocyanate groups are reacted (“blocked”) with a materialsuch as epsilon-caprolactone and methylethyl ketoxime. At curingtemperatures, the blocking agents unblock exposing isocyanatefunctionality that is reactive with the hydroxyl functionalityassociated with the (meth)acrylic polymer. Blocked polyisocyanatecrosslinking agents are commercially available from Covestro as DESMODURBL.

Examples of polyepoxide crosslinking agents are epoxy-containing(meth)acrylic polymers such as those prepared from glycidyl methacrylatecopolymerized with other vinyl monomers, polyglycidyl ethers ofpolyhydric phenols such as the diglycidyl ether of bisphenol A; andcycloaliphatic polyepoxides such as3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate andbis(3,4-epoxy-6-methylcyclohexyl-methyl) adipate.

In addition to promoting the cross-linking of the dispersant, thecrosslinking agents, including those associated with crosslinkingmonomers and separately added crosslinking agents, react with thehydrophilic groups, such as active hydrogen functional groups of thedispersant preventing these groups from absorbing moisture that could beproblematic in a lithium ion battery.

The separately added crosslinker may be present in the binder in amountsof up to 15% by weight, such as 1% to 15% by weight, the % by weightbeing based on the total weight of the binder solids.

The binder typically has a resin solids content of from 30% to 80% byweight, such as 40% to 70% by weight, based on the total weight of thebinder dispersion. As used herein, the term “resin solids” may be usedsynonymously with “binder solids” and include the fluoropolymer,adhesion promoter, and, if present, the dispersant, and separately addedcrosslinking agent. As used herein, the term “binder dispersion” refersto a dispersion of the binder solids in the liquid medium. Thefluoropolymer may be present in in the binder in amounts of 40% to 96%by weight, such as 50% to 90% by weight; the adhesion promoter may bepresent in the slurry composition in an amount of 10% to 60% by weight,20% to 60% by weight, such as 30% to 60% by weight, such as 10% to 50%by weight, such as 15% to 40% by weight, such as 20% to 30% by weight,such as 35% to 35% by weight; the dispersant may be present in amountsof 2% to 20% by weight, such as 5% to 15% by weight; and the separatelyadded crosslinker may be present in amounts of up to 15% by weight, suchas 1% to 15% by weight, the % by weight being based on the total weightof the binder solids. The liquid medium is present in the binderdispersion in amounts of 20% to 70% by weight, such as 30% to 60% byweight, based on total weight of the binder dispersion.

The binder solids may be present in the slurry in amounts of 1% to 20%by weight, such as 1% to 10% by weight, such as 5% to 10% percent byweight, based on the total solids weight of the slurry.

The slurry composition of the present invention may optionally furthercomprise an electrically conductive agent. Non-limiting examples ofelectrically conductive agents include carbonaceous materials such as,activated carbon, carbon black such as acetylene black and furnaceblack, graphite, graphene, carbon nanotubes, carbon fibers, fullerene,and combinations thereof. The electrically conductive material may alsocomprise any active carbon that has a high-surface area, such as a BETsurface area of greater than 100 m²/g. As used herein, the term “BETsurface area” refers to a specific surface area determined by nitrogenadsorption according to the ASTM D 3663-78 standard based on theBrunauer-Emmett-Teller method described in the periodical “The Journalof the American Chemical Society”, 60, 309 (1938). In some examples, theconductive carbon can have a BET surface area of 100 m²/g to 1,000 m²/g,such as 150 m²/g to 600 m²/g, such as 100 m²/g to 400 m²/g, such as 200m²/g to 400 m²/g. In some examples, the conductive carbon can have a BETsurface area of about 200 m²/g. A suitable conductive carbon material isLITX 200 commercially available from Cabot Corporation. The conductivecarbon material can be present in the slurry in amounts of 2 to 20,typically 5 to 10 percent by weight based on total solids weight of theslurry.

The electrically conductive agent may be present in the slurry inamounts of 1% to 20% by weight, such as 5% to 10% by weight, based onthe total solids weight of the slurry.

The slurry composition may be in the form of an electrode slurrycomposition comprising the binder, electrochemically active material andelectrically conductive material, each as described above. The electrodeslurry may comprise such materials present in the slurry composition inthe amounts described above. For example, the electrode slurrycomposition may comprise the electrochemically active material presentin amounts of 45% to 95% by weight, such as 70% to 98% by weight; thebinder present in amounts of 1% to 20% by weight, such as 1% to 10% byweight, such as 5% to 10% percent by weight; and the electricallyconductive agent present in amounts of 1% to 20% by weight, such as 5%to 10% by weight, the percentages by weight based on the total solidsweight of the electrode slurry composition.

The electrode slurry composition comprising the liquid medium,electrochemically active material, electrically conductive material,binder dispersion (which may include a separately added crosslinkingagent), additional liquid medium, if needed, and optional ingredients,may be prepared by combining the ingredients to form the slurry. Thesesubstances can be mixed together by agitation with a known means such asa stirrer, bead mill or high-pressure homogenizer.

As for mixing and agitation for the manufacture of the electrode slurrycomposition, a mixer capable of stirring these components to such anextent that satisfactory dispersion conditions are met should beselected. The degree of dispersion can be measured with a particle gaugeand mixing and dispersion are preferably carried out to ensure thatagglomerates of 100 microns or more are not present. Examples of themixers which meets this condition include ball mill, sand mill, pigmentdisperser, grinding machine, extruder, rotor stator, pug mill,ultrasonic disperser, homogenizer, planetary mixer, Hobart mixer, andcombinations thereof.

The slurry composition may have a solids content of at least 30% byweight, such as at least 40% by weight, such as at least 50% by weight,such as at least 55%, such as at least 60%, such as at least 65%, suchas at least 71%, such as at least 75%, and may be no more than 90% byweight, such as no more than 85% by weight, such as no more than 75% byweight, the % by weight based on the total weight of the slurrycomposition. The slurry composition may have a solids content of 30% to90% by weight, such as 40% to 85% by weight, such as 50% to 85% byweight, such as 55% to 85% by weight, such as 60% to 85% by weight, suchas 65% to 85% by weight, such as 71% to 85% by weight, such as 75% to85% by weight, based on the total weight of the slurry composition.

The present invention is also directed to an electrode comprising anelectrical current collector and a film formed on the electrical currentcollector, wherein the film is deposited from the electrode slurrycomposition described above. The electrode may be a positive electrodeor a negative electrode and may be manufactured by applying theabove-described slurry composition to the surface of the currentcollector to form a coating film, and subsequently drying and/or curingthe coating film. The coating film may have a thickness of at least 1micron, such as 1 to 500 microns (μm), such as 1 to 150 μm, such as 25to 150 μm, such as 30 to 125 μm. The coating film may comprise across-linked coating. The current collector may comprise a conductivematerial, and the conductive material may comprise a metal such as iron,copper, aluminum, nickel, and alloys thereof, as well as stainlesssteel. For example, the current collector may comprise aluminum orcopper in the form of a mesh, sheet or foil. Although the shape andthickness of the current collector are not particularly limited, thecurrent collector may have a thickness of about 0.001 to 0.5 mm, such asa mesh, sheet or foil having a thickness of about 0.001 to 0.5 mm.

The coating film produced from the slurry composition of the presentinvention may possess improved adhesion to the current collectorcompared to a coating film produced from a slurry composition that doesnot include the adhesion promoter of the present invention. For example,the use of the coating film resulting from the slurry composition of thepresent invention may improve adhesion by at least 50%, such as at least100%, such as at least 200%, such as at least 300%, such as at least400%, compared to a coating film produced from a slurry composition thatdoes not include the adhesion promoter of the present invention. As usedherein, the term “adhesion” refers to peel strength adhesion as measuredby the PEEL STRENGTH TEST METHOD. According to the PEEL STRENGTH TESTMETHOD, adhesion is measured using a motorized test stand (EMS-303,available from Mark-10) equipped with a 10 N force gauge (Series 5,Model M5-2) and a 90° peel stage. The lateral movement of the 90° peelstage is actively driven at the same rate as the vertical movement ofthe test stand crosshead, which ensures a 90° peel angle throughout theentire measurement. A coating on aluminum foil, prepared as described inthe Examples section below, is cut into rectangular strips (1.1 incheswide by 11 inches long). The coated side of the strips are adhered to arigid aluminum substrate using 3M 444 double-sided tape (1 inch wide by7 inches long), leaving a free end of the foil that was not taped down.The rigid aluminum substrate is then fastened to the 90° peel stage, andthe free end of the foil is secured in the peel stage grips such that a90° angle is achieved between the instrument crosshead and the peelstage. The samples are then peeled at a rate of 50 mm/min for 2 min.

The current collector may be pretreated with a pretreatment compositionprior to depositing the slurry composition. As used herein, the term“pretreatment composition” refers to a composition that upon contactwith the current collector, reacts with and chemically alters thecurrent collector surface and binds to it to form a protective layer.The pretreatment composition may be a pretreatment compositioncomprising a group IIIB and/or IVB metal. As used herein, the term“group IIIB and/or IVB metal” refers to an element that is in group IIIBor group IVB of the CAS Periodic Table of the Elements as is shown, forexample, in the Handbook of Chemistry and Physics, 63^(rd) edition(1983). Where applicable, the metal themselves may be used, however, agroup IIIB and/or IVB metal compound may also be used. As used herein,the term “group IIIB and/or IVB metal compound” refers to compounds thatinclude at least one element that is in group TIM or group IVB of theCAS Periodic Table of the Elements. Suitable pretreatment compositionsand methods for pretreating the current collector are described in U.S.Pat. No. 9,273,399 at col. 4, line 60 to col. 10, line 26, the citedportion of which is incorporated herein by reference. The pretreatmentcomposition may be used to treat current collectors used to producepositive electrodes or negative electrodes.

The method of applying the slurry composition to the current collectoris not particularly limited. The slurry composition may be applied bydoctor blade coating, dip coating, reverse roll coating, direct rollcoating, gravure coating, extrusion coating, immersion or brushing.Although the application quantity of the slurry composition is notparticularly limited, the thickness of the coating formed after theliquid medium is removed may be 25 to 150 microns (μm), such as 30 to125 μm.

Drying and/or crosslinking the coating film after application, ifapplicable, can be done, for example, by heating at elevatedtemperature, such as at least 50° C., such as at least 60° C., such as50-145° C., such as 60-120° C., such as 65-110° C. The time of heatingwill depend somewhat on the temperature. Generally, higher temperaturesrequire less time for curing. Typically, curing times are for at least 5minutes, such as 5 to 60 minutes. The temperature and time should besufficient such that the dispersant in the cured film is crosslinked (ifapplicable), that is, covalent bonds are formed between co-reactivegroups on the dispersant polymer chain, such as carboxylic acid groupsand hydroxyl groups and the N-methylol and/or the N-methylol ethergroups of an aminoplast, isocyanato groups of a blocked polyisocyanatecrosslinking agent, or in the case of a self-curing dispersant, theN-alkoxymethyl amide groups or blocked isocyanato groups. The extent ofcure or crosslinking may be measured as resistance to solvents such asmethyl ethyl ketone (MEK). The test is performed as described in ASTMD-540293. The number of double rubs, one back and forth motion, isreported. This test is often referred to as “MEK Resistance”.Accordingly, the dispersant and crosslinking agent (inclusive ofself-curing dispersants and dispersants with separately addedcrosslinking agents) is isolated from the binder composition, depositedas a film and heated for the temperature and time that the binder filmis heated. The film is then measured for MEK Resistance with the numberof double rubs reported. Accordingly, a crosslinked dispersant will havean MEK Resistance of at least 50 double rubs, such as at least 75 doublerubs. Also, the crosslinked dispersant may be substantially solventresistant to the solvents of the electrolyte mentioned below. Othermethods of drying the coating film include ambient temperature drying,microwave drying and infrared drying, and other methods of curing thecoating film include e-beam curing and UV curing.

During discharge of a lithium ion electrical storage device, lithiumions may be released from the negative electrode and carry the currentto the positive electrode. This process may include the process known asdeintercalation. During charging, the lithium ions migrate from theelectrochemically active material in the positive electrode to thenegative electrode where they become embedded in the electrochemicallyactive material present in the negative electrode. This process mayinclude the process known as intercalation.

The present invention is also directed to an electrical storage device.An electrical storage device according to the present invention can bemanufactured by using the above electrodes prepared from the electrodeslurry composition of the present invention. The electrical storagedevice comprises an electrode, a counter electrode and an electrolyte.The electrode, counter-electrode or both may comprise the electrode ofthe present invention, as long as one electrode is a positive electrodeand one electrode is a negative electrode. Electrical storage devicesaccording to the present invention include a cell, a battery, a batterypack, a secondary battery, a capacitor, and a supercapacitor.

The electrical storage device includes an electrolytic solution and canbe manufactured by using parts such as a separator in accordance with acommonly used method. As a more specific manufacturing method, anegative electrode and a positive electrode are assembled together witha separator there between, the resulting assembly is rolled or bent inaccordance with the shape of a battery and put into a battery container,an electrolytic solution is injected into the battery container, and thebattery container is sealed up. The shape of the battery may be like acoin, button or sheet, cylindrical, square or flat.

The electrolytic solution may be liquid or gel, and an electrolyticsolution which can serve effectively as a battery may be selected fromamong known electrolytic solutions which are used in electrical storagedevices in accordance with the types of a negative electrode activematerial and a positive electrode active material. The electrolyticsolution may be a solution containing an electrolyte dissolved in asuitable solvent. The electrolyte may be conventionally known lithiumsalt for lithium ion secondary batteries. Examples of the lithium saltinclude LiClO₄, LiBF₄, LiPF₆, LiCF₃CO₂, LiAsF₆, LiSbF₆, LiB₁₀Cl₁₀,LiAlCl₄, LiCl, LiBr, LiB(C₂H₅)₄, LiB(C₆H₅)₄, LiCF₃SO₃, LiCH₃SO₃,LiC₄F₉SO₃, Li(CF₃SO₂)₂N, LiB₄CH₃SO₃Li and CF₃SO₃Li. The solvent fordissolving the above electrolyte is not particularly limited andexamples thereof include carbonate compounds such as propylenecarbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate,methyl ethyl carbonate and diethyl carbonate; lactone compounds such asγ-butyl lactone; ether compounds such as trimethoxymethane,1,2-dimethoxyethane, diethyl ether, 2-ethoxyethane, tetrahydrofuran and2-methyltetrahydrofuran; and sulfoxide compounds such as dimethylsulfoxide. The concentration of the electrolyte in the electrolyticsolution may be 0.5 to 3.0 mole/L, such as 0.7 to 2.0 mole/L.

As used herein, the term “polymer” refers broadly to oligomers and bothhomopolymers and copolymers. The term “resin” is used interchangeablywith “polymer”.

The terms “acrylic” and “acrylate” are used interchangeably (unless todo so would alter the intended meaning) and include acrylic acids,anhydrides, and derivatives thereof, such as their C₁-C₅ alkyl esters,lower alkyl-substituted acrylic acids, e.g., C₁-C₂ substituted acrylicacids, such as methacrylic acid, 2-ethylacrylic acid, etc., and theirC₁-C₄ alkyl esters, unless clearly indicated otherwise. The terms“(meth)acrylic” or “(meth)acrylate” are intended to cover both theacrylic/acrylate and methacrylic/methacrylate forms of the indicatedmaterial, e.g., a (meth)acrylate monomer. The term “(meth)acrylicpolymer” refers to polymers prepared from one or more (meth)acrylicmonomers.

As used herein molecular weights are determined by gel permeationchromatography using a polystyrene standard. Unless otherwise indicatedmolecular weights are on a weight average basis.

The term “glass transition temperature” as used herein is a theoreticalvalue being the glass transition temperature as calculated by the methodof Fox on the basis of monomer composition of the monomer chargeaccording to T. G. Fox, Bull. Am. Phys. Soc. (Ser. II) 1, 123 (1956) andJ. Brandrup, E. H. Immergut, Polymer Handbook 3^(rd) edition, JohnWiley, New York, 1989.

As used herein, unless otherwise defined, the term substantially freemeans that the component is present, if at all, in an amount of lessthan 5% by weight, based on the total weight of the slurry composition.

As used herein, unless otherwise defined, the term essentially freemeans that the component is present, if at all, in an amount of lessthan 1% by weight, based on the total weight of the slurry composition.

As used herein, unless otherwise defined, the term completely free meansthat the component is not present in the slurry composition, i.e., 0.00%by weight, based on the total weight of the slurry composition.

As used herein, the term “total solids” refers to the non-volatilecomponents of the slurry composition of the present invention andspecifically excludes the liquid medium.

As used herein, the term “consists essentially of” includes the recitedmaterial or steps and those that do not materially affect the basic andnovel characteristics of the claimed invention.

As used herein, the term “consists of” excludes any element, step oringredient not recited.

For purposes of the detailed description, it is to be understood thatthe invention may assume various alternative variations and stepsequences, except where expressly specified to the contrary. Moreover,other than in any operating examples, or where otherwise indicated, allnumbers such as those expressing values, amounts, percentages, ranges,subranges and fractions may be read as if prefaced by the word “about,”even if the term does not expressly appear. Accordingly, unlessindicated to the contrary, the numerical parameters set forth in thefollowing specification and attached claims are approximations that mayvary depending upon the desired properties to be obtained by the presentinvention. At the very least, and not as an attempt to limit theapplication of the doctrine of equivalents to the scope of the claims,each numerical parameter should at least be construed in light of thenumber of reported significant digits and by applying ordinary roundingtechniques. Where a closed or open-ended numerical range is describedherein, all numbers, values, amounts, percentages, subranges andfractions within or encompassed by the numerical range are to beconsidered as being specifically included in and belonging to theoriginal disclosure of this application as if these numbers, values,amounts, percentages, subranges and fractions had been explicitlywritten out in their entirety.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contains certainerrors necessarily resulting from the standard variation found in theirrespective testing measurements.

As used herein, unless indicated otherwise, a plural term can encompassits singular counterpart and vice versa, unless indicated otherwise. Forexample, although reference is made herein to “an” electrochemicallyactive material, “a” fluoropolymer, “a” dispersant, and “an”electrically conductive agent, “an” adhesion promoter, a combination(i.e., a plurality) of these components can be used. In addition, inthis application, the use of “or” means “and/or” unless specificallystated otherwise, even though “and/or” may be explicitly used in certaininstances.

As used herein, “including,” “containing” and like terms are understoodin the context of this application to be synonymous with “comprising”and are therefore open-ended and do not exclude the presence ofadditional undescribed or unrecited elements, materials, ingredients ormethod steps. As used herein, “consisting of” is understood in thecontext of this application to exclude the presence of any unspecifiedelement, ingredient or method step. As used herein, “consistingessentially of” is understood in the context of this application toinclude the specified elements, materials, ingredients or method steps“and those that do not materially affect the basic and novelcharacteristic(s)” of what is being described. Although variousembodiments of the invention have been described in terms of“comprising”, embodiments consisting essentially of or consisting of arealso within the scope of the present invention.

As used herein, the terms “on,” “onto,” “applied on,” “applied onto,”“formed on,” “deposited on,” “deposited onto,” mean formed, overlaid,deposited, or provided on but not necessarily in contact with thesurface. For example, a composition “deposited onto” a substrate doesnot preclude the presence of one or more other intervening coatinglayers of the same or different composition located between theelectrodepositable coating composition and the substrate.

Whereas specific embodiments of the invention have been described indetail, it will be appreciated by those skilled in the art that variousmodifications and alternatives to those details could be developed inlight of the overall teachings of the disclosure. Accordingly, theparticular arrangements disclosed are meant to be illustrative only andnot limiting as to the scope of the invention which is to be given thefull breadth of the claims appended and any and all equivalents thereof.

Aspects

Each of the characteristics and examples described above, andcombinations thereof, may be said to be encompassed by the presentinvention. The present invention is thus drawn in particular, withoutbeing limited thereto, to the following aspects:

1. A slurry composition comprising:

(a) a binder comprising a polymer comprising a fluoropolymer dispersedin a liquid medium;

(b) an adhesion promoter; and at least one of

(c1) an electrochemically active material, and

(c2) an electrically conductive agent.

2. The slurry composition of Aspect 1, wherein the adhesion promotercomprises a polyvinylidene fluoride copolymer different from thefluoropolymer of the binder.

3. The slurry composition of Aspect 2, wherein the polyvinylidenefluoride copolymer comprises constitutional units comprising the residueof vinylidene fluoride and at least one of:

(i) (meth)acrylic acid; or

(ii) hydroxyalkyl (meth)acrylate.

4. The slurry composition of Aspect 3, wherein the (meth)acrylic acidcomprises acrylic acid.

5. The slurry composition of Aspects 3 or 4, wherein the hydroxyalkyl(meth)acrylate comprises a C₁ to C₅ hydroxyalkyl (meth)acrylate.

6. The slurry composition of Aspect 5, wherein the C₁ to C₅ hydroxyalkyl(meth)acrylate comprises hydroxyethyl (meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl (meth)acrylate, or combinations thereof.

7. The slurry composition of Aspects 3 to 6, wherein the adhesionpromoter comprises 50% to 99% by moles of constitutional unitscomprising the residue of vinylidene fluoride, such as 70% to 98% bymoles, such as 80% to 95% by moles; and 0.01% to 10% by moles ofconstitutional units comprising the residue of the (meth)acrylic acid,such as 0.02% to 5% by moles, such as 0.03% to 2% by moles, based on thetotal molar content of the polyvinylidene fluoride copolymer adhesionpromoter.

8. The slurry composition of Aspects 3 to 6, wherein the adhesionpromoter comprises 50% to 99% by moles of constitutional unitscomprising the residue of vinylidene fluoride, such as 70% to 98% bymoles, such as 80% to 95% by moles; and 0.01% to 10% by moles ofconstitutional units comprising the residue of the hydroxyalkyl(meth)acrylate, such as 0.02% to 5% by moles, such as 0.03% to 2% bymoles, based on the total molar content of the polyvinylidene fluoridecopolymer adhesion promoter.

9. The slurry composition of Aspects 3 to 6, wherein the adhesionpromoter comprises 50% to 99% by moles of constitutional unitscomprising the residue of vinylidene fluoride, such as 70% to 98% bymoles, such as 80% to 95% by moles; 0.01% to 10% by moles ofconstitutional units comprising the residue of the (meth)acrylic acid,such as 0.02% to 5% by moles, such as 0.03% to 2% by moles; and 0.01% to10% by moles of constitutional units comprising the residue of thehydroxyalkyl (meth)acrylate, such as 0.02% to 5% by moles, such as 0.03%to 2% by moles, based on the total molar content of the polyvinylidenefluoride copolymer adhesion promoter.

10. The slurry composition of any of Aspects 2 to 9, wherein the liquidmedium comprises an organic medium.

11. The slurry composition of Aspect 10, wherein the organic medium hasan evaporation rate less than 10 g/min m², at the dissolutiontemperature of the fluoropolymer in the organic medium.

12. The slurry composition of Aspects 10 or 11, wherein the organicmedium has an evaporation rate greater than 80 g/min m², at 180° C.

13. The slurry composition of any one of Aspects 2 to 12, wherein theorganic medium comprises butyl pyrrolidone, trialkyl phosphate such astriethylphosphate, 1,2,3-triacetoxypropane,3-methoxy-N,N-dimethylpropanamide, ethyl acetoacetate,gamma-butyrolactone, propylene glycol methyl ether, cyclohexanone,propylene carbonate, dimethyl adipate, propylene glycol methyl etheracetate, dibasic ester (DBE), dibasic ester 5,4-hydroxy-4-methyl-2-pentanone, propylene glycol diacetate, dimethylphthalate, methyl isoamyl ketone, ethyl propionate, 1-ethoxy-2-propanol,dipropylene glycol dimethyl ether, saturated and unsaturated linear andcyclic ketones, diisobutyl ketone, acetate esters, tripropylene glycolmethyl ether, diethylene glycol ethyl ether acetate, or combinationsthereof.

14. The slurry composition of any one of Aspects 2 to 13, wherein theorganic medium comprises a primary solvent and a co-solvent, the primarysolvent comprising butyl pyrrolidone, a trialkylphosphate such astriethylphosphate, 3-methoxy-N,N-dimethylpropanamide,1,2,3-triacetoxypropane, or combinations thereof, and the co-solventcomprising ethyl acetoacetate, gamma-butyrolactone, propylene glycolmethyl ether, dipropylene glycol methyl ether, propylene glycolmonopropyl ether, diethylene glycol monobutyl ether, ethylene glycolmonohexyl ether, or combinations thereof.

15. The slurry composition of Aspect 14, wherein the primary solvent ispresent in an amount of 50% to 99% by weight, such as 65% to 90% byweight, such as 75% to 85% by weight, and the co-solvent is present inan amount of 1% to 50% by weight, such as 10% to 35% by weight, such as15% to 25% by weight, each based on the total weight of the organicmedium.

16. The slurry composition of any of one of Aspects 13 to 15, where theorganic medium comprises triethyl phosphate.

17. The slurry composition of Aspects 14 or 15, wherein the organicmedium comprises triethyl phosphate as the primary solvent and ethylacetoacetate as a co-solvent.

18. The slurry composition of Aspect 1, wherein the adhesion promotercomprises an acid-functional polyolefin.

19. The slurry composition of Aspect 18, wherein the acid-functionalpolyolefin comprises an ethylene-acrylic acid copolymer.

20. The slurry composition of Aspect 19, wherein the ethylene-acrylicacid copolymer comprises constitutional units comprising 20% by weightacrylic acid, based on the total weight of the ethylene-acrylic acidcopolymer.

21. The slurry composition of any one of Aspects 18 to 20, wherein theliquid medium comprises an aqueous medium.

22. The slurry composition of any one of Aspects 1 to 21, wherein theelectrically conductive agent comprises graphite, carbon black such asacetylene black and furnace black, graphene, carbon nanotubes, orcombinations thereof.

23. The slurry composition of any one of Aspects 1 to 21, wherein theelectrically conductive agent comprises conductive carbon materialhaving a BET surface area of 100 m²/g to 1000 m²/g.

24. The slurry composition of any one of Aspects 1 to 23, wherein theslurry is substantially free of isophorone.

25. The slurry composition of any one of Aspects 1 to 24, wherein theslurry is substantially free of N-methyl-2-pyrrolidone.

26. The slurry composition of any of the preceding Aspects, wherein thebinder solids are present in the slurry composition in amounts of 1% to20% by weight, such as 1% to 10% by weight, such as 5% to 10% percent byweight, based on the total solids weight of the slurry, based on thetotal solids weight of the slurry.

27. The slurry composition of any one of Aspects 1 to 25, wherein theadhesion promoter is present in the slurry composition in an amount of10% to 60% by weight, such as 20% to 60% by weight, such as 30% to 60%by weight, such as 10% to 50% by weight, such as 15% to 40% by weight,such as 20% to 30% by weight, or such as 35% to 35% by weight, based onthe total weight of the binder solids.

28. The slurry composition of any one of Aspects 1 to 25, wherein thebinder solids are present in the slurry composition in amounts of 1% to20% by weight, such as 1% to 10% by weight, such as 5% to 10% percent byweight, based on the total solids weight of the slurry, and thefluoropolymer is present in the binder in amounts of 40% to 96% byweight, such as 50% to 90% by weight; the dispersant is present inamounts of 2% to 20% by weight, such as 5% to 15% by weight; and theadhesion promoter is present in the slurry composition in an amount of10% to 60% by weight, 20% to 60% by weight, such as 30% to 60% byweight, such as 10% to 50% by weight, such as 15% to 40% by weight, suchas 20% to 30% by weight, such as 35% to 35% by weight, the % by weightbeing based on the total weight of the binder solids.

29. The slurry composition of any one of Aspects 1 to 25, wherein thebinder solids are present in the slurry composition in amounts of 1% to20% by weight, such as 1% to 10% by weight, such as 5% to 10% percent byweight, based on the total solids weight of the slurry, and thefluoropolymer is present in the binder in amounts of 40% to 96% byweight, such as 50% to 90% by weight; the dispersant is present inamounts of 2% to 20% by weight, such as 5% to 15% by weight; theadhesion promoter is present in the slurry composition in an amount of10% to 60% by weight, 20% to 60% by weight, such as 30% to 60% byweight, such as 10% to 50% by weight, such as 15% to 40% by weight, suchas 20% to 30% by weight, such as 35% to 35% by weight; and theseparately added crosslinker may be present in amounts of up to 15% byweight, such as 1% to 15% by weight, the % by weight being based on thetotal weight of the binder solids.

30. The slurry composition of any of the preceding Aspects, wherein theelectrochemically active material comprises a material capable ofincorporating lithium.

31. The slurry composition of Aspect 30, wherein material capable ofincorporating lithium comprises LiCoO₂, LiNiO₂, LiFePO₄, LiCoPO₄,LiMnO₂, LiMn₂O₄, Li(NiMnCo)O₂, Li(NiCoAl)O₂, carbon-coated LiFePO₄, or acombination thereof.

32. The slurry composition of any of Aspects 1 to 29, wherein theelectrochemically active material comprises a material capable oflithium conversion.

33. The slurry composition of Aspect 32, wherein the material capable oflithium conversion comprises sulfur, LiO₂, FeF₂ and FeF₃, Si, aluminum,tin, SnCo, Fe₃O₄, or combinations thereof.

34. The slurry composition of any of Aspects 1 to 29, wherein theelectrochemically active material comprises graphite, silicon compounds,tin, tin compounds, sulfur, sulfur compounds, or a combination thereof.

35. The slurry composition of any of the preceding Aspects, wherein theelectrochemically active material is present in the slurry compositionin amounts of 45% to 95% by weight, such as 70% to 98% by weight, basedon the total solids weight of the slurry.

36. The slurry composition of any of the preceding Aspects, wherein theelectrically conductive agent is present in the slurry composition inamounts of 1% to 20% by weight, such as 5% to 10% by weight, based onthe total solids weight of the slurry.

37. An electrode comprising:

(a) an electrical current collector; and

(b) a film formed on the electrical current collector, wherein the filmis deposited from the slurry composition of any one of the precedingAspects.

38. The electrode of Aspect 37, wherein the electrical current collector(a) comprises copper or aluminum in the form of a mesh, sheet or foil.

39. The electrode of Aspects 37 or 38, wherein the electrode comprises apositive electrode.

40. The electrode of Aspects 37 or 38, wherein the electrode comprises anegative electrode.

41. The electrode of any one of Aspects 37 to 40, wherein the film iscross-linked.

42. The electrode of any one of Aspects 37 to 41, wherein the electricalcurrent collector is pretreated with a pretreatment composition.

43. The electrode of any one of Aspect 37 to 42, wherein the film has athickness of at least 1 μm, such as 1 to 500 μm, such as 1 to 150 μm,such as 25 to 150 μm, such as 30 to 125 μm.

44. An electrical storage device comprising:

(a) the electrode of any one of Aspects 37 to 43;

(b) a counter electrode; and

(c) an electrolyte.

45. The electrical storage device of Aspect 44, wherein the electrolyte(c) comprises a lithium salt dissolved in a solvent.

46. The electrical storage device of Aspect 45, wherein the lithium saltis dissolved in an organic carbonate.

47. The electrical storage device of any one of Aspects 44 to 46,wherein the electrical storage device comprises a cell.

48. The electrical storage device of any one of Aspects 44 to 46,wherein the electrical storage device comprises a battery pack.

49. The electrical storage device of any one of Aspects 44 to 46,wherein the electrical storage device comprises a secondary battery.

50. The electrical storage device of any one of Aspects 44 to 46,wherein the electrical storage device comprises a capacitor.

51. The electrical storage device of any one of Aspects 44 to 46,wherein the electrical storage device comprises a supercapacitor.

Illustrating the invention are the following examples, which, however,are not to be considered as limiting the invention to their details.Unless otherwise indicated, all parts and percentages in the followingexamples, as well as throughout the specification, are by weight.

EXAMPLES Example 1 Synthesis of a (meth)acrylic Copolymer Dispersantwith Theoretical Glass Transition (Tg) of 3.5° C.

Amount Ingredients (gram) Charge 1: diacetone alcohol 280 Charge 2:t-amyl peroctoate 6.54 (premixed) diacetone alcohol 116.8 Charge 3:methyl methacrylate 207.5 (premixed) ethyl acrylate 194.5 methacrylicacid 54.5 butyl acrylate 215 Charge 4: diacetone alcohol 33.5 Charge 5:t-amyl peroctoate 2.0 (premixed) diacetone alcohol 36 Charge 6:diacetone alcohol 16 Charge 7: dimethyl ethanol amine 60.2 Charge 8: 70°C. deionized water 1695.5

To a suitable reaction vessel equipped with a stirrer, reflux condenser,thermometer, heating mantle and nitrogen inlet, Charge 1 was added atambient temperature. The temperature was then increased to a set-pointof 122° C., at which time the initiator premix of Charge 2 was addedover 210 minutes and Charge 3 was added over 180 minutes. Uponcompletion of the addition of Charge 2, Charge 4 was added and thereaction vessel was held for 60 minutes at a set point of 122° C. Charge5 was then added over 30 minutes, followed by the addition of Charge 6and an additional 90-minute hold at a set point of 122° C. After coolingto below 100° C., Charge 7 was added over 10 minutes and stirring wascontinued for 15 minutes before Charge 8 was added over 90 minutes.Thereafter the reaction temperature was cooled to 50° C. The dispersantcomposition thus formed had a theoretical solids content of 23.25% byweight.

Solids contents of dispersant compositions were measured in eachdispersant example by the following procedure. An aluminum weighing dishfrom Fisher Scientific, was weighed using an analytical balance. Theweight of the empty dish was recorded to four decimal places.Approximately 0.5 g of dispersant and 3.5 g of acetone was added to theweigh dish. The weight of the dish and the dispersant solution wasrecorded to four decimal places. The dish containing the dispersantsolution was placed into a laboratory oven, with the oven temperatureset to 110° C., and dried for 1 hour. The weigh dish and drieddispersant was weighed using an analytical balance. The weight of thedish and dried dispersant was recorded to four decimal places. Thesolids was determined using the following equation: %solids=100×[(weight of the dish and the dry dispersant)−(weight of theempty dish)]/[(weight of the dish and the dispersant solution)−(weightof the empty dish)].

Example 2 Preparation of Binder Dispersion

In a 1-liter plastic container, was placed 23.3 grams of deionizedwater, 225.7 grams of the dispersant composition from Example 1, and0.47 grams of Drewplus Y-281 defoamer (available from Ashland). Theresultant mixture was stirred vigorously using a Cowles blade. Thismixing was continued while 150.5 grams of polyvinylidene difluoridepowder, PG-11 (available from Arkema) was added gradually. Mixing wascontinued for an additional 20 minutes after all the polyvinylidenedifluoride powder was added. Resimene HM-2608 melamine crosslinkingagent (available from Ineos Melamines, LLC) was then added to the binderdispersion at a dry solids weight ratio of PVDF:dispersant:melamine of70/25/5.

Example 3 (Comparative) Preparation of Binder Solution in NMP

To a plastic container was added solvent grade N-methyl-2-pyrrolidone(available from Ashland, 1141.44 grams). While stirring with a Cowlesblade, polyvinylidene difluoride, Kynar HSV-900 (available from Arkema,58.56 grams) was added in portions. Stirring was continued until thepolymer was completely dissolved.

Example 4 Adhesion Promoter Composition

Amount Ingredients (gram) Charge 1: Primacor 5980i (ethylene - acrylicacid copolymer) 1441.2 available from Dow Chemical Co.) Deionized water3603.0 Charge 2: Dimethylethanolamine 356.56 Charge 3: Deionized water1805.24

To a suitable reaction vessel equipped with a stirrer, reflux condenser,thermometer, heating mantle and nitrogen inlet, Charge 1 was added atambient temperatures. Under continuous mixing, the temperature was thenincreased to 40° C. over 20 minutes. After mixing for 20 minutes at 40°C., Charge 2 was added over 5 minutes. The reaction vessel was thenheated to 75° C. over 15 minutes. Charge 3 was then added over 10minutes and the reaction vessel was heated to 90° C. over 40 minutes.The batch was further heated to 95° C. over 30 minutes and mixed foranother 30 minutes. The batch was then cooled down and filtered with a5-micron filter. The composition had a theoretical solids content of 20%by weight.

Solids contents for all compositions other than the dispersantcompositions were measured by the following procedure. An aluminumweighing dish from Fisher Scientific, was weighed using an analyticalbalance. The weight of the empty dish was recorded to four decimalplaces. Approximately 1 g of dispersion was added to the weigh dish. Theweight of the dish and the wet dispersion was recorded to four decimalplaces. The dish containing the slurry was placed into a laboratoryoven, with the oven temperature set to 120 degrees centigrade, and driedfor 1 hour. The weigh dish and dried dispersion was weighed using ananalytical balance. The weight of the dish and dried slurry was recordedto four decimal places. The solids was determined using the followingequation: % solids=100×[(weight of the dish and the drydispersion)−(weight of the empty dish)]/[(weight of the dish and the wetdispersion)−(weight of the empty dish)].

Example 5 (Comparative) Preparation of Cathodes Using a Waterborne PVDFDispersion that Contains an Adhesion Promoter at 0% of the Total BinderPackage (Percent by Weight, Based on the Total Weight of Resin Solids inthe Binder)

To a plastic cup was added 1.69 grams of ethanol, 21.97 grams ofdeionized water, 1.06 grams of the binder dispersion from Example 2, and1.16 grams of sodium hydroxide neutralized Acrysol ASE-60 (acidcontaining, cross-linked acrylic emulsion copolymer thickener, availablefrom The Dow Chemical Company). This blend was placed in adual-asymmetric centrifugal mixer and mixed at 2000 rpm for 5 minutes.After mixing, 28.62 grams of cathode active powder lithium nickelmanganese cobalt oxide (NCM 111, available from BASF) was added to themixture, and the resulting combination was mixed in a dual-asymmetriccentrifugal mixer at 2000 rpm for 5 minutes. After mixing, 2.54 grams ofTimcal C-NERGY™ Super C65 conductive carbon (available from TIMCAL) wasadded, and the blend was placed in a dual-asymmetric centrifugal mixerand mixed at 2000 rpm for 10 minutes. Next, 2.26 grams of ButylCELLOSOLVE™ glycol ether and 0.71 grams of DOWANOL™ PnB glycol ether(both available from the Dow Chemical Co.) was added and the mixture wasmixed on a dual-asymmetric centrifugal mixer at 2000 rpm for 5 minutes.

A wet film was prepared on aluminum foil by a draw-down application ofthis formulated slurry using a doctor blade. This wet film was flashedfor 15 minutes at 25° C., then heated in an oven to a temperature of 60°C. for at least 30 minutes, and then heated in an oven to maximumtemperature of 246° C. for 10 minutes. After cooling, an average dryfilm thickness of 53 microns was determined from five measurements witha micrometer.

Battery performance data and peel strength for this coating is shown inTable 1.

Example 6 Preparation of Electrodes Using a Waterborne Binder Dispersionthat Contains an Adhesion Promoter at 10% of the Total Binder Package,(Percent by Weight, Based on the Total Weight of Resin Solids in theBinder)

To a plastic cup was added 1.15 grams of ethanol, 13.75 grams of DIwater, 1.20 grams of the binder dispersion from Example 2, 1.49 grams ofsodium hydroxide neutralized Acrysol ASE-60, and 0.41 grams of theadhesion promoter composition from Example 4. This blend was placed in adual-asymmetric centrifugal mixer and mixed at 2000 rpm for 5 minutes.After mixing, 36.72 grams of cathode active powder lithium nickelmanganese cobalt oxide NMC-111 (electrochemically active material(Li(NiMnCo)O₂), available from BASF) was added to the mixture, and theresulting combination was mixed in a dual-asymmetric centrifugal mixerat 2000 rpm for 5 minutes. After mixing, 3.26 grams of Timcal C-NERGY™Super C65 conductive carbon was added, and the blend was placed in adual-asymmetric centrifugal mixer and mixed at 2000 rpm for 10 minutes.Next, 1.54 grams of Butyl CELLOSOLVE™ glycol ether and 0.48 grams ofDOWANOL™ PnB glycol ether was added and the mixture was mixed on adual-asymmetric centrifugal mixer at 2000 rpm for 5 minutes.

A wet film was prepared on pre-cleaned aluminum foil by a draw-downapplication of this formulated slurry using a doctor blade. This wetfilm was flashed for 15 minutes at 25° C., then heated in an oven to atemperature of 60° C. for at least 30 minutes, and then heated in anoven to maximum temperature of 246° C. for 10 minutes. After cooling, anaverage dry film thickness of 52 microns was determined from fivemeasurements with a micrometer. Battery performance data and peelstrength for this electrode is shown in Table 1.

Example 7 Preparation of Electrode Using a Waterborne PVDF Dispersionthat Contains an Adhesion Promoter at 30% of the Total Binder Package,(Percent by Weight, Based on the Total Weight of Resin Solids in theBinder)

To a plastic cup was added 0.90 grams of ethanol, 9.43 grams of DIwater, 0.99 grams of the binder dispersion from Example 2, 1.65 grams ofsodium hydroxide neutralized Acrysol ASE-60 (available from the DowChemical Co.) and 1.35 grams of the adhesion promoter composition fromExample 4. This blend was placed in a dual-asymmetric centrifugal mixerand mixed at 2000 rpm for 5 minutes. After mixing, 40.50 grams ofcathode active powder NMC-111 was added to the mixture, and theresulting combination was mixed in a dual-asymmetric centrifugal mixerat 2000 rpm for 5 minutes. After mixing, 3.60 grams of Timcal C-NERGY™Super C65 conductive carbon was added, and the blend was placed in adual-asymmetric centrifugal mixer and mixed at 2000 rpm for 10 minutes.Next, 1.20 grams of Butyl CELLOSOLVE™ glycol ether and 0.37 grams ofDOWANOL™ PnB glycol ether was added and the mixture was mixed on adual-asymmetric centrifugal mixer at 2000 rpm for 5 minutes.

A wet film was prepared on pre-cleaned aluminum foil by a draw-downapplication of this formulated slurry using a doctor blade. This wetfilm was flashed for 15 minutes at 25° C., then heated in an oven to atemperature of 60° C. for at least 30 minutes, and then heated in anoven to maximum temperature of 246° C. for 10 minutes. After cooling, anaverage dry film thickness of 52 microns was determined from fivemeasurements with a micrometer. Battery performance data and peelstrength for this coating is shown in Table 1.

Example 8 Preparation of Electrode Using a Waterborne PVDF Dispersionthat Contains an Adhesion Promoter at 60% of the Total Binder Package,(Percent by Weight, Based on the Total Weight of Resin Solids in theBinder)

To a plastic cup was added 0.90 grams of ethanol, 8.42 grams of DIwater, 0.49 grams of the binder dispersion from Example 2, 1.81 grams ofsodium hydroxide neutralized Acrysol ASE-60, and 2.70 grams of theadhesion promoter composition from Example 4. This blend was placed in adual-asymmetric centrifugal mixer and mixed at 2000 rpm for 5 minutes.After mixing, 40.50 grams of cathode active powder NMC-111 was added tothe mixture, and the resulting combination was mixed in adual-asymmetric centrifugal mixer at 2000 rpm for 5 minutes. Aftermixing, 3.60 grams of Timcal C-NERGY™ Super C65 conductive carbon wasadded, and the blend was placed in a dual-asymmetric centrifugal mixerand mixed at 2000 rpm for 10 minutes. Next, 1.20 grams of ButylCELLOSOLVE™ glycol ether and 0.37 grams of DOWANOL™ PnB glycol ether wasadded and the mixture was mixed on a dual-asymmetric centrifugal mixerat 2000 rpm for 5 minutes.

A wet film was prepared on pre-cleaned aluminum foil by a draw-downapplication of this formulated slurry using a doctor blade. This wetfilm was flashed for 15 minutes at 25° C., then heated in an oven to atemperature of 60° C. for at least 30 minutes, and then heated in anoven to maximum temperature of 246° C. for 10 minutes. After cooling, anaverage dry film thickness of 49 microns was determined from fivemeasurements with a micrometer. Battery performance data and peelstrength for this coating is shown in Table 1.

Example 9 Preparation of Electrode Using a Waterborne PVDF Dispersionthat Contains an Adhesion Promoter at 100% of the Total Binder Package,(Percent by Weight, Based on the Total Weight of Resin Solids in theBinder)

To a plastic cup was added 0.79 grams of ethanol, 7.28 grams of DIwater, and 4.68 grams of the acrylic acid-ethylene copolymer dispersionfrom Example 4. This blend was placed in a dual-asymmetric centrifugalmixer and mixed at 2000 rpm for 5 minutes. After mixing, 42.12 grams ofcathode active powder lithium nickel manganese cobalt oxide (NCM 111)was added to the mixture, and the resulting combination was mixed in adual-asymmetric centrifugal mixer at 2000 rpm for 5 minutes. Aftermixing, 3.74 grams of Timcal C-NERGY™ Super C65 conductive carbon wasadded, and the blend was placed in a dual-asymmetric centrifugal mixerand mixed at 2000 rpm for 10 minutes. Next, 1.06 grams of ButylCELLOSOLVE™ glycol ether and 0.33 grams of DOWANOL™ PnB glycol ether wasadded and the mixture was mixed on a dual-asymmetric centrifugal mixerat 2000 rpm for 5 minutes.

A wet film was prepared on pre-cleaned aluminum foil by a draw-downapplication of this formulated slurry using a doctor blade. This wetfilm was flashed for 15 minutes at 25° C., then heated in an oven to atemperature of 60° C. for at least 30 minutes, and then heated in anoven to maximum temperature of 246° C. for 10 minutes. After cooling, anaverage dry film thickness of 52 microns was determined from fivemeasurements with a micrometer. Battery performance data and peelstrength for this coating is shown in Table 1 below.

Example 10 (Comparative) Preparation of Cathodes Using the ComparativeBinder Solution Made of PVDF Dissolved in NMP (Example 3)

To a plastic cup was added NMP (25.22 grams), binder solution fromExample 3 (10.08 grams) and conductive carbon C-NERGY™ Super C65 (2.02grams). This blend was placed in a dual-asymmetric centrifugal mixer andmixed at 2000 rpm for 10 minutes. Cathode active powder NMC-111 (22.68grams) was added to this mixed blend, and the resulting combination wasmixed in a dual-asymmetric centrifugal mixer at 2000 rpm for 10 minutesto produce a formulated slurry.

A wet film was prepared on pre-cleaned aluminum foil by a draw-downapplication of this formulated slurry using a doctor blade. This wetfilm was heated in an oven to a maximum temperature of 150° C. for atleast 5 minutes. After cooling, an average dry film thickness of 38microns was determined from five measurements with a micrometer. Batteryperformance data and peel strength for this coating is shown in Table 1.

Peel strength test procedure: Peel strength was measured using the PEELSTRENGTH TEST METHOD and is reported in Table 1.

Coin cell testing procedure: The dry coated foils were passed through aroll calendar press (Innovative Machine Corporation) to achieve 25-30%compression. After vacuum drying, two coin-type half-cell batteries perdry coated foil were assembled using lithium metal as the negativeelectrode and one-molar LiPF6 in ethylene carbonate, diethyl carbonateand dimethyl carbonate solvents as the electrolyte. The coin cellbatteries were then tested on a battery tester (Arbin Instruments) usinga potential window of 4.2-3 Volts for 5 cycles each at currentscorresponding to 0.2 C, 0.4 C, 0.8 C, 1.6 C, 3.2 C and 6.4 Ccharge/discharge rates, followed by 50 cycles at the currentcorresponding to a 1 C rate. Discharge capacity in milliamp-hours pergram of lithium nickel manganese cobalt oxide 1:1:1 was calculated fromthe average of the first 5 cycles for each C-rate. “C-rate” refers to acurrent value that is required to fully discharge a cell having aconstant electric capacitance in a time period equal to the inverse ofthe C-rate value in hours. For example, discharge capacity at 0.2 Crefers to dry coated film capacity in milliamp-hours per gram of lithiumnickel manganese cobalt oxide at a current value required to fullydischarge the battery in 5 hours. Similarly discharge capacity at 1 Crefers to dry coated film capacity in milliamp-hours per gram of lithiumnickel manganese cobalt oxide at a current value required to fullydischarge the battery in 1 hour.

Discharge capacity averages from the higher capacity coin-type half-cellof the two replicate cells for a given dry coated foil are reported inTable 1. Capacity retention was calculated from the quotient of thedischarge capacity after the first charge-discharge cycle at 1 C and thelast charge-discharge cycle at 1 C and reported as percentage accordingto the equation: 100×first cycle capacity/last cycle capacity.

Table 1 shows the peel force of 1″ wide electrodes and discharge datafor coin-cell batteries prepared from Example electrodes. The tableshows cell specific capacity (milliamp-hours per gram) for variousdischarge C-rates (per hour).

TABLE 1 % Capacity Retention Peel after about Force Discharge C-Rate(hour⁻¹) 42 cycles at Example (mN) 0.2 0.4 0.8 1.6 3.2 6.4 1.0 C-rate of1.0 5 102 152 148 140 135 126 112 140 99.6 6 161 7 618 154 151 145 139129 110 144 100 8 726 9 968 151 148 142 134 120 86 140 101 10 549 155152 147 141 134 123 146 99.3

Example 11 Synthesis of (meth)acrylic Polymer Dispersant withTheoretical Glass Transition Temperature (Tg) of −12.4° C.

Amount Ingredients (gram) Charge 1: Triethylphosphate 375.4 Charge 2:Triethylphosphate 61.1 (premixed) Tertiary amyl peroxy 2-ethoxy hexylcarbonate 12.9 Charge 3: methyl methacrylate 228.2 (premixed) ethylacrylate 91.6 methacrylic acid 0 hydroxyethyl acrylate 11.5 ethylhexylacrylate 193.8 glycidyl methacrylate 58.4 Charge 4: Triethylphosphate21.99 Charge 5: Tertiary amyl peroxy 2-ethoxy hexyl carbonate 4.3(premixed) Triethylphosphate 61.17 Charge 6: Triethylphosphate 57.9

To a suitable reaction vessel equipped with a stirrer, condenser,thermometer, heating mantle and nitrogen inlet, Charge 1 was added atambient temperatures. The temperature was then increased to 120° C., atwhich time the initiator premix of Charge 2 was added over 185 minutes.Five minutes after the start of Charge 2, Charge 3 was added over 180minutes. Upon completion of Charges 2 and 3, Charge 4 was added,followed by Charge 5 added over 60 minutes, followed by Charge 6 and anadditional 60-minute hold at 120° C. After cooling to below 90° C., thedispersant composition thus formed had a theoretical solids content of51.32% by weight.

Example 12 Synthesis of Acrylic Polymer Dispersant with TheoreticalGlass Transition Temperature (Tg) of −12.2° C.

This polymer was prepared the same way as the polymer of Example 11,except Charge 3 consisted of the following monomers:

Charge 3: methyl methacrylate 228.2 (premixed) ethyl acrylate 58.4methacrylic acid 11.5 Hydroxyethyl acrylate 11.5 Ethylhexyl acrylate215.7 Vinyl Pyrrolidone 58.4

Example 13 Synthesis of (meth)acrylic Polymer Dispersant withTheoretical Glass Transition (Tg) of −12.4°

This polymer was prepared the same way as the polymer of Example 11except Charge 3 consisted of the following monomers:

Charge 3: methyl methacrylate 228.2 (premixed) ethyl acrylate 157.0methacrylic acid 11.5 Hydroxyethyl acrylate 11.5 Ethylhexyl acrylate175.3

Examples 14-16 Formulation of Binder Dispersions

In a 2-liter plastic container, was placed 41.64 grams oftriethylphosphate, 26.85 grams of (meth)acrylic copolymer dispersantcomposition from Example 12. The resultant mixture was stirredvigorously using a Cowles blade while maintaining a modest vortex. Thismixing was continued while 32.90 grams of polyvinylidene difluoridepowder, PVDF T-1 (Inner Mongolia 3F Wanhao Fluorochemical Co., Ltd) wasadded in small portions. Mixing was continued for an additional 30minutes after all the polyvinylidene difluoride powder was added.

By similar procedures, as shown in the table below, PVDF dispersionswere prepared from combinations of (meth)acrylic copolymer dispersantcompositions and PVDF at the specified weight ratios.

Acrylic polymer (Meth)acrylic PVDF weight weight percent of CopolymerPolyvinylidene percent of dry dry solid Example from: Difluoride solidcomponents components Example Example 11 PVDF T-1 70.9 29.1 14 ExampleExample 12 PVDF T-1 69.7 30.3 15 Example None Kynar HSV 900 100 0 16(Arkema)

Example 17 (Comparative) Preparation of Electrode Using a Slurry with NoAdhesion Promoter

To a plastic cup was added triethylphosphate (14.83 grams), the binderdispersion from Example 15 (2.15 grams). Conductive carbon LITX200 (0.72grams, available from Cabot Corp.) was added in two portions with eachsequential blend mixed in a dual-asymmetric centrifugal mixer at 2000rpm for 5 minutes. Cathode active powder NMC-111 (22.33 grams) was addedin two portions to this mixed blend, with each sequential blend mixed ina dual-asymmetric centrifugal mixer at 2000 rpm for 5 minutes to produceformulated slurry. The total non-volatiles content of this slurry was60%. The final ratio of NMC-111:LITX200:Binder dry solids was 93:3:4.

A wet film was prepared on pre-cleaned aluminum foil by a draw-downapplication of this formulated slurry using a doctor blade. This wetfilm was heated in an oven to a maximum temperature of 120° C. for atleast 10 minutes. After cooling, an average dry film thickness of 106microns was determined from five measurements with a micrometer. The dryfilm was pressed in a pinch-roller calender press (Innovative MachineCo.) to a film thickness of 87 microns. The resultant film's adhesionwas tested was measured using the PEEL STRENGTH TEST METHOD. Tested assuch, the coating demonstrated a 90-degree peel strength of 7.9 N/m.

Example 18 Slurry Composition and Electrode

To a plastic cup was added triethylphosphate (12.46 grams), the binderdispersion from Example 15 (1.83 grams), and an adhesion promotercomposition of vinylidene fluoride-acrylic acid copolymer (Solef 5130available from Solvay) dissolved in triethylphosphate at 5.40% w/w (2.68grams). Conductive carbon LITX200 (0.72 grams) was added in two portionswith each sequential blend mixed in a dual-asymmetric centrifugal mixerat 2000 rpm for 5 minutes. Cathode active powder NMC-111 (22.32 grams)was added in two portions to this mixed blend, with each sequentialblend mixed in a dual-asymmetric centrifugal mixer at 2000 rpm for 5minutes to produce formulated slurry. The total non-volatiles content ofthis slurry was 60% by weight. The final weight ratio ofNMC-111:LITX200:Binder dry solids was 93:3:4.

A wet film was prepared on pre-cleaned aluminum foil by a draw-downapplication of this formulated slurry using a doctor blade. This wetfilm was heated in an oven to a maximum temperature of 120° C. for atleast 10 minutes. After cooling, an average dry film thickness of 109microns was determined from five measurements with a micrometer. The dryfilm was calender-pressed to a film thickness of 90 microns anddemonstrated a 90-degree peel strength of 16.7 N/m as measured using thePEEL STRENGTH TEST METHOD.

Example 19 Slurry Composition and Electrode

To a plastic cup was added triethylphosphate (10.13 grams), the binderdispersion from Example 15 (1.51 grams), and an adhesion promotercomposition of vinylidene fluoride-acrylic acid copolymer (Solef 5130)dissolved in triethylphosphate at 5.40% w/w (5.33 grams). Conductivecarbon LITX200 (0.72 grams) was added in two portions with eachsequential blend mixed in a dual-asymmetric centrifugal mixer at 2000rpm for 5 minutes. Cathode active powder NMC-111 (22.33 grams) was addedin two portions to this mixed blend, with each sequential blend mixed ina dual-asymmetric centrifugal mixer at 2000 rpm for 5 minutes to produceformulated slurry. The total non-volatiles content of this slurry was60% by weight. The final weight ratio of NMC-111:LITX200:Binder drysolids was 93:3:4.

A wet film was prepared on pre-cleaned aluminum foil by a draw-downapplication of this formulated slurry using a doctor blade. This wetfilm was heated in an oven to a maximum temperature of 120° C. for atleast 10 minutes. After cooling, an average dry film thickness of 106microns was determined from five measurements with a micrometer. The dryfilm was calender-pressed to a film thickness of 88 microns anddemonstrated a 90-degree peel strength of 29.3 N/m as measured using thePEEL STRENGTH TEST METHOD.

Example 20

To a plastic cup was added triethylphosphate (7.00 grams), the binderdispersion from Example 15 (1.08 grams), and an adhesion promotercomposition of vinylidene fluoride-acrylic acid copolymer (Solef 5130)dissolved in triethylphosphate at 5.40% w/w (8.89 grams). Conductivecarbon LITX200 (0.72 grams) was added in two portions with eachsequential blend mixed in a dual-asymmetric centrifugal mixer at 2000rpm for 5 minutes. Cathode active powder NMC-111 (22.34 grams) was addedin two portions to this mixed blend, with each sequential blend mixed ina dual-asymmetric centrifugal mixer at 2000 rpm for 5 minutes to produceformulated slurry. The total non-volatiles content of this slurry was60% by weight. The final weight ratio of NMC-111:LITX200:Binder drysolids was 93:3:4.

A wet film was prepared on pre-cleaned aluminum foil by a draw-downapplication of this formulated slurry using a doctor blade. This wetfilm was heated in an oven to a maximum temperature of 120° C. for atleast 10 minutes. After cooling, an average dry film thickness of 106microns was determined from five measurements with a micrometer. The dryfilm was calender-pressed to a film thickness of 90 microns anddemonstrated a 90-degree peel strength of 39.0 N/m as measured using thePEEL STRENGTH TEST METHOD.

Example 21

To a plastic cup was added triethylphosphate (1.87 grams), the binderdispersion from Example 16 (0.77 grams), an adhesion promotercomposition of vinylidene fluoride-acrylic acid copolymer (Solef 5130)dissolved in triethylphosphate at 6.30% w/w (1.49 grams), and thedispersant composition from Example 11 diluted to 0.63% w/w intriethylphosphate (15.52 grams). Conductive carbon LITX200 (1.66 grams)was added in two portions with each sequential blend mixed in adual-asymmetric centrifugal mixer at 2000 rpm for 5 minutes. Cathodeactive powder NMC-111 (18.72 grams) was added in two portions to thismixed blend, with each sequential blend mixed in a dual-asymmetriccentrifugal mixer at 2000 rpm for 5 minutes to produce formulatedslurry. The total non-volatiles content of this slurry was 52% byweight. The final weight ratio of NMC-111:LITX200:Binder dry solids was90:8:2.

A wet film was prepared on pre-cleaned aluminum foil by a draw-downapplication of this formulated slurry using a doctor blade. This wetfilm was heated in an oven to a maximum temperature of 120° C. for atleast 10 minutes. After cooling, an average dry film thickness of 65microns was determined from five measurements with a micrometer. The dryfilm was calender-pressed to a film thickness of 45 microns anddemonstrated a 90-degree peel strength of 9.8 N/m as measured using thePEEL STRENGTH TEST METHOD.

Example 22

To a plastic cup was added triethylphosphate (9.41 grams), the binderdispersion from Example 16 (0.53 grams), an adhesion promotercomposition of vinylidene fluoride-acrylic acid copolymer (Solef 5130)dissolved in triethylphosphate at 6.30% w/w (3.59 grams), and thedispersant composition from Example 11, diluted to 0.63% w/w intriethylphosphate (6.21 grams). Conductive carbon LITX200 (1.66 grams)was added in two portions with each sequential blend mixed in adual-asymmetric centrifugal mixer at 2000 rpm for 5 minutes. Cathodeactive powder NMC-111 (18.75 grams) was added in two portions to thismixed blend, with each sequential blend mixed in a dual-asymmetriccentrifugal mixer at 2000 rpm for 5 minutes to produce formulatedslurry. The total non-volatiles content of this slurry was 52% byweight. The final weight ratio of NMC-111:LITX200:Binder dry solids was90:8:2.

A wet film was prepared on pre-cleaned aluminum foil by a draw-downapplication of this formulated slurry using a doctor blade. This wetfilm was heated in an oven to a maximum temperature of 120° C. for atleast 10 minutes. After cooling, an average dry film thickness of 70microns was determined from five measurements with a micrometer. The dryfilm was calender-pressed to a film thickness of 49 microns anddemonstrated a 90-degree peel strength of 15.4 N/m as measured using thePEEL STRENGTH TEST METHOD.

Example 23

To a plastic cup was added triethylphosphate (0.69 grams), the binderdispersion from Example 16 (0.43 grams), an adhesion promotercomposition of vinylidene fluoride-acrylic acid copolymer (Solef 5130)dissolved in triethylphosphate at 6.30% w/w (2.98 grams), and thedispersant composition from Example 11 diluted to 0.63% w/w intriethylphosphate (15.56 grams). Conductive carbon LITX200 (1.67 grams)was added in two portions with each sequential blend mixed in adual-asymmetric centrifugal mixer at 2000 rpm for 5 minutes. Cathodeactive powder NMC-111 (18.76 grams) was added in two portions to thismixed blend, with each sequential blend mixed in a dual-asymmetriccentrifugal mixer at 2000 rpm for 5 minutes to produce formulatedslurry. The total non-volatiles content of this slurry was 52% byweight. The final weight ratio of NMC-111:LITX200:Binder dry solids was90:8:2.

A wet film was prepared on pre-cleaned aluminum foil by a draw-downapplication of this formulated slurry using a doctor blade. This wetfilm was heated in an oven to a maximum temperature of 120° C. for atleast 10 minutes. After cooling, an average dry film thickness of 66microns was determined from five measurements with a micrometer. The dryfilm was calender-pressed to a film thickness of 47 microns anddemonstrated a 90-degree peel strength of 5.5 N/m as measured using thePEEL STRENGTH TEST METHOD.

Example 24

To a plastic cup was added triethylphosphate (10.73 grams), the binderdispersion from Example 16 (0.90 grams), an adhesion promotercomposition of vinylidene fluoride-acrylic acid copolymer (Solef 5130)dissolved in triethylphosphate at 6.30% w/w (1.78 grams), and thedispersant composition from Example 11 diluted to 0.63% w/w intriethylphosphate (6.24 grams). Conductive carbon LITX200 (1.67 grams)was added in two portions with each sequential blend mixed in adual-asymmetric centrifugal mixer at 2000 rpm for 5 minutes. Cathodeactive powder NMC-111 (18.78 grams) was added in two portions to thismixed blend, with each sequential blend mixed in a dual-asymmetriccentrifugal mixer at 2000 rpm for 5 minutes to produce formulatedslurry. The total non-volatiles content of this slurry was 52% byweight. The final weight ratio of NMC-111:LITX200:Binder dry solids was90:8:2.

A wet film was prepared on pre-cleaned aluminum foil by a draw-downapplication of this formulated slurry using a doctor blade. This wetfilm was heated in an oven to a maximum temperature of 120° C. for atleast 10 minutes. After cooling, an average dry film thickness of 72microns was determined from five measurements with a micrometer. The dryfilm was calender-pressed to a film thickness of 52 microns anddemonstrated a 90-degree peel strength of 12.5 N/m as measured using thePEEL STRENGTH TEST METHOD.

Example 25

To a plastic cup was added triethylphosphate (13.95 grams), the binderdispersion from Example 16 (0.56 grams), an adhesion promotercomposition of vinylidene fluoride-acrylic acid copolymer (Solef 5130)dissolved in triethylphosphate at 6.30% w/w (2.60 grams), and thedispersant composition from Example 11 (0.09 grams). Conductive carbonDenka Black (1.46 grams) was added in two portions with each sequentialblend mixed in a dual-asymmetric centrifugal mixer at 2000 rpm for 5minutes. Cathode active powder NMC-111 (16.40 grams) was added in twoportions to this mixed blend, with each sequential blend mixed in adual-asymmetric centrifugal mixer at 2000 rpm for 5 minutes to produceformulated slurry. The total non-volatiles content of this slurry was52% by weight. The final weight ratio of NMC-111:Denka Black:Binder drysolids was 90:8:2.

A wet film was prepared on pre-cleaned aluminum foil by a draw-downapplication of this formulated slurry using a doctor blade. This wetfilm was heated in an oven to a maximum temperature of 120° C. for atleast 10 minutes. After cooling, an average dry film thickness of 95microns was determined from five measurements with a micrometer. The dryfilm was calender-pressed to a film thickness of 52 microns anddemonstrated a 90-degree peel strength of 2.2 N/m as measured using thePEEL STRENGTH TEST METHOD.

Example 26 (Comparative) Preparation of Electrode Using a Slurry with NoBinder or Dispersant

To a plastic cup was added triethylphosphate (2.53 grams) and anadhesion promoter composition of vinylidene fluoride-acrylic acidcopolymer (Solef 5130) dissolved in triethylphosphate at 5.00% w/w(13.45 grams). Conductive carbon LITX200 (0.51 grams) was added in oneportion and the blend mixed in a dual-asymmetric centrifugal mixer at2000 rpm for 5 minutes. Cathode active powder NMC-111 (15.62 grams) wasadded in two portions to this mixed blend, with each sequential blendmixed in a dual-asymmetric centrifugal mixer at 2000 rpm for 5 minutesto produce formulated slurry. The total non-volatiles content of thisslurry was 52% by weight. The final weight ratio ofNMC-111:LITX200:Binder dry solids was 93:3:4.

A wet film was prepared on pre-cleaned aluminum foil by a draw-downapplication of this formulated slurry using a doctor blade. This wetfilm was heated in an oven to a maximum temperature of 120° C. for atleast 10 minutes. After cooling, an average dry film thickness of 89microns was determined from five measurements with a micrometer. The dryfilm was calender-pressed to a film thickness of 65 microns anddemonstrated a 90-degree peel strength of 60.4 N/m as measured using thePEEL STRENGTH TEST METHOD.

Example 27 (Comparative) Preparation of Electrode Using a Slurry with NoAdhesion Promoter

To a plastic cup was added triethylphosphate (14.71 grams) and thebinder dispersion from Example 14 (2.27 grams). Conductive carbonLITX200 (0.72 grams) was added in two portions with each sequentialblend mixed in a dual-asymmetric centrifugal mixer at 2000 rpm for 5minutes. Cathode active powder NMC-111 (22.33 grams) was added in twoportions to this mixed blend, with each sequential blend mixed in adual-asymmetric centrifugal mixer at 2000 rpm for 5 minutes to produceformulated slurry. The total non-volatiles content of this slurry was60% by weight. The final weight ratio of NMC-111:LITX200:Binder drysolids was 93:3:4.

A wet film was prepared on pre-cleaned aluminum foil by a draw-downapplication of this formulated slurry using a doctor blade. This wetfilm was heated in an oven to a maximum temperature of 68° C. for atleast 10 minutes. After cooling, an average dry film thickness of 74microns was determined from five measurements with a micrometer. The dryfilm was calender-pressed to a film thickness of 57 microns anddemonstrated a 90-degree peel strength of 11.2 N/m as measured using thePEEL STRENGTH TEST METHOD.

Example 28

To a plastic cup was added triethylphosphate (12.37 grams), the binderdispersion from Example 14 (1.93 grams) and an adhesion promotercomposition of vinylidene fluoride-acrylic acid copolymer (Solef 5130)dissolved in triethylphosphate at 5.40% w/w (2.67 grams). Conductivecarbon LITX200 (0.72 grams) was added in two portions with eachsequential blend mixed in a dual-asymmetric centrifugal mixer at 2000rpm for 5 minutes. Cathode active powder NMC-111 (22.32 grams) was addedin two portions to this mixed blend, with each sequential blend mixed ina dual-asymmetric centrifugal mixer at 2000 rpm for 5 minutes to produceformulated slurry. The total non-volatiles content of this slurry was60% by weight. The final weight ratio of NMC-111:LITX200:Binder drysolids was 93:3:4.

A wet film was prepared on pre-cleaned aluminum foil by a draw-downapplication of this formulated slurry using a doctor blade. This wetfilm was heated in an oven to a maximum temperature of 68° C. for atleast 10 minutes. After cooling, an average dry film thickness of 74microns was determined from five measurements with a micrometer. The dryfilm was calender-pressed to a film thickness of 56 microns anddemonstrated a 90-degree peel strength of 36.5 N/m as measured using thePEEL STRENGTH TEST METHOD.

Example 29

To a plastic cup was added triethylphosphate (10.04 grams), the binderdispersion from Example 14 (1.58 grams), and an adhesion promotercomposition of vinylidene fluoride-acrylic acid copolymer (Solef 5130)dissolved in triethylphosphate at 5.40% w/w (5.33 grams). Conductivecarbon LITX200 (0.72 grams) was added in two portions with eachsequential blend mixed in a dual-asymmetric centrifugal mixer at 2000rpm for 5 minutes. Cathode active powder NMC-111 (22.33 grams) was addedin two portions to this mixed blend, with each sequential blend mixed ina dual-asymmetric centrifugal mixer at 2000 rpm for 5 minutes to produceformulated slurry. The total non-volatiles content of this slurry was60% by weight. The final weight ratio of NMC-111:LITX200:Binder drysolids was 93:3:4.

A wet film was prepared on pre-cleaned aluminum foil by a draw-downapplication of this formulated slurry using a doctor blade. This wetfilm was heated in an oven to a maximum temperature of 68° C. for atleast 10 minutes. After cooling, an average dry film thickness of 75microns was determined from five measurements with a micrometer. The dryfilm was calender-pressed to a film thickness of 57 microns anddemonstrated a 90-degree peel strength of 51.6 N/m as measured using thePEEL STRENGTH TEST METHOD.

Example 30

To a plastic cup was added triethylphosphate (6.95 grams), the binderdispersion from Example 14 (1.14 grams), an adhesion promotercomposition of vinylidene fluoride-acrylic acid copolymer (Solef 5130)dissolved in triethylphosphate at 5.40% w/w (8.90 grams). Conductivecarbon LITX200 (0.73 grams) was added in two portions with eachsequential blend mixed in a dual-asymmetric centrifugal mixer at 2000rpm for 5 minutes. Cathode active powder NMC-111 (22.33 grams) was addedin two portions to this mixed blend, with each sequential blend mixed ina dual-asymmetric centrifugal mixer at 2000 rpm for 5 minutes to produceformulated slurry. The total non-volatiles content of this slurry was60% by weight. The final weight ratio of NMC-111:LITX200:Binder drysolids was 93:3:4.

A wet film was prepared on pre-cleaned aluminum foil by a draw-downapplication of this formulated slurry using a doctor blade. This wetfilm was heated in an oven to a maximum temperature of 68° C. for atleast 10 minutes. After cooling, an average dry film thickness of 72microns was determined from five measurements with a micrometer. The dryfilm was calender-pressed to a film thickness of 56 microns anddemonstrated a 90-degree peel strength of 79.9 N/m as measured using thePEEL STRENGTH TEST METHOD.

Examples 17-20 demonstrate that the addition of more adhesion promoteryields higher peel strength than dispersed PVDF alone for 93:3:4 usingLITX 200 conductive carbon. Examples 21-24 demonstrate that an adhesionpromoter yields higher peel strength in 90:8:2 with LITX/NMC. Example 25demonstrates that an adhesion promoter yields higher peel strength withDenka black in 90:8:2. Example 26 (Comparative) demonstrates that anadhesion promoter alone in TEP does not yield high peel strength usingNMC & LITX at 93:3:4. Examples 27-30 demonstrate that more adhesionpromoter yields higher peel strength than dispersed PVDF alone for93:3:4 using LITX 20 conductive carbon, but this time with a lower baketemp and thinner films.

It will be appreciated by skilled artisans that numerous modificationsand variations are possible in light of the above disclosure withoutdeparting from the broad inventive concepts described and exemplifiedherein. Accordingly, it is therefore to be understood that the foregoingdisclosure is merely illustrative of various exemplary aspects of thisapplication and that numerous modifications and variations can bereadily made by skilled artisans which are within the spirit and scopeof this application and the accompanying claims.

What is claimed is:
 1. A slurry composition comprising: (a) anelectrochemically active material; (b) a binder comprising a polymercomprising a fluoropolymer dispersed in an organic medium; and (c) anadhesion promoter, wherein the slurry composition is substantially freeof N-methyl-2-pyrrolidone, and wherein the organic medium comprises lessthan 50% by weight water, based on total weight of the organic medium.2. The slurry composition of claim 1, wherein the adhesion promotercomprises a polyvinylidene fluoride copolymer.
 3. The slurry compositionof claim 2, wherein the polyvinylidene fluoride copolymer comprisesconstitutional units comprising the residue of vinylidene fluoride andat least one of: (i) (meth)acrylic acid; or (ii) hydroxyalkyl(meth)acrylate.
 4. The slurry composition of claim 3, wherein the(meth)acrylic acid comprises acrylic acid.
 5. The slurry composition ofclaim 3, wherein the hydroxyalkyl (meth)acrylate comprises a C₁ to C₅hydroxyalkyl (meth)acrylate.
 6. The slurry composition of claim 5,wherein the C₁ to C₅ hydroxyalkyl (meth)acrylate comprises hydroxyethyl(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl(meth)acrylate, or combinations thereof.
 7. The slurry composition ofclaim 1, wherein the organic medium has an evaporation rate less than 10grams per square meter per minute, at a dissolution temperature of thefluoropolymer dispersed in the organic medium.
 8. The slurry compositionof claim 1, wherein the organic medium has an evaporation rate greaterthan 80 grams per square meter per minute, at 180° C.
 9. The slurrycomposition of claim 1, wherein the organic medium comprises butylpyrrolidone, trialkyl phosphate, 1,2,3-triacetoxypropane,3-methoxy-N,N-dimethylpropanamide, ethyl acetoacetate,gamma-butyrolactone, propylene glycol methyl ether, cyclohexanone,propylene carbonate, dimethyl adipate, propylene glycol methyl etheracetate, dibasic ester (DBE), dibasic ester 5,4-hydroxy-4-methyl-2-pentanone, propylene glycol diacetate, dimethylphthalate, methyl isoamyl ketone, ethyl propionate, 1-ethoxy-2-propanol,dipropylene glycol dimethyl ether, saturated and unsaturated linear andcyclic ketones, diisobutyl ketone, acetate esters, tripropylene glycolmethyl ether, diethylene glycol ethyl ether acetate, or combinationsthereof.
 10. The slurry composition of claim 1, wherein the organicmedium comprises a primary solvent and a co-solvent, the primary solventcomprising butyl pyrrolidone, a trialkylphosphate,3-methoxy-N,N-dimethylpropanamide, 1,2,3-triacetoxypropane, orcombinations thereof, and the co-solvent comprising ethyl acetoacetate,gamma-butyrolactone, propylene glycol methyl ether, dipropylene glycolmethyl ether, propylene glycol monopropyl ether, diethylene glycolmonobutyl ether, ethylene glycol monohexyl ether, or combinationsthereof.
 11. The slurry composition of claim 1, wherein the adhesionpromoter comprises an acid-functional polyolefin.
 12. The slurrycomposition of claim 11, wherein the acid-functional polyolefincomprises an ethylene-acrylic acid copolymer.
 13. The slurry compositionof claim 11, wherein the ethylene-acrylic acid copolymer comprisesconstitutional units comprising 20% by weight acrylic acid, based on thetotal weight of the ethylene-acrylic acid copolymer.
 14. The slurrycomposition of claim 1, further comprising an electrically conductiveagent.
 15. The slurry composition of claim 14, wherein the electricallyconductive agent comprises graphite, acetylene black, furnace black,graphene, carbon nanotubes, or combinations thereof.
 16. The slurrycomposition of claim 14, wherein the electrically conductive agentcomprises conductive carbon material having a surface area of 100 m²/gto 1000 m²/g.
 17. The slurry composition of claim 1, wherein the slurryis essentially free of isophorone.
 18. A slurry composition comprising:(a) an electrically conductive agent; (b) a binder comprising a polymercomprising a fluoropolymer dispersed in an organic medium; and (c) anadhesion promoter, wherein the slurry composition is substantially freeof N-methyl-2-pyrrolidone, and wherein the organic medium comprises lessthan 50% by weight water, based on total weight of the organic medium.19. An electrode comprising: (a) an electrical current collector; and(b) a film formed on the electrical current collector, wherein the filmis deposited from the slurry composition of claim
 14. 20. The electrodeof claim 19, wherein the electrical current collector (a) comprisescopper or aluminum in the form of a mesh, sheet or foil.
 21. Theelectrode of claim 19, wherein the electrode comprises a positiveelectrode.
 22. The electrode of claim 19, wherein the electrodecomprises a negative electrode.
 23. The electrode of claim 19, whereinthe film is cross-linked.
 24. The electrode of claim 19, wherein theelectrical current collector is pretreated with a pretreatmentcomposition.
 25. An electrical storage device comprising: (a) electrodeof claim 19; (b) a counter electrode; and (c) an electrolyte.
 26. Theelectrical storage device of claim 25, wherein the electrolyte (c)comprises a lithium salt dissolved in a solvent.
 27. The electricalstorage device of claim 26, wherein the lithium salt is dissolved in anorganic carbonate.
 28. The electrical storage device of claim 25,wherein the electrical storage device comprises a cell.
 29. Theelectrical storage device of claim 25, wherein the electrical storagedevice comprises a battery pack.
 30. The electrical storage device ofclaim 25, wherein the electrical storage device comprises a secondarybattery.
 31. The electrical storage device of claim 25, wherein theelectrical storage device comprises a capacitor.
 32. The electricalstorage device of claim 25, wherein the electrical storage devicecomprises a supercapacitor.
 33. The slurry composition of claim 1,wherein the organic medium comprises at least 70% by weight organicsolvent, based on the total weight of the organic medium.
 34. The slurrycomposition of claim 18, wherein the organic medium comprises at least70% by weight organic solvent, based on the total weight of the organicmedium.